Phase-dependent growth of Pt on MoS2 for highly efficient H2 evolution.

Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs)1,2. The TMD materials, explored for diverse applications3-8, commonly serve as templates for constructing nanomaterials3,9 and supported metal catalysts4,6-8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS2 nanosheets used as electrocatalysts for the hydrogen evolution reaction7, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS2 template composed of the metallic/semimetallic 1T/1T' phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS2 nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T' phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T'-MoS2 system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H2 evolution in acidic media, where we measure for s-Pt/1T'-MoS2 a mass activity of 85 ± 23 A [Formula: see text] at the overpotential of -50 mV and a mass-normalized exchange current density of 127 A [Formula: see text] and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T'-TMDs will also be effective supports for other catalysts targeting other important reactions.

Liquid-activated quantum emission from pristine hexagonal boron nitride for nanofluidic sensing.

Liquids confined down to the atomic scale can show radically new properties. However, only indirect and ensemble measurements operate in such extreme confinement, calling for novel optical approaches that enable direct imaging at the molecular level. Here we harness fluorescence originating from single-photon emitters at the surface of hexagonal boron nitride for molecular imaging and sensing in nanometrically confined liquids. The emission originates from the chemisorption of organic solvent molecules onto native surface defects, revealing single-molecule dynamics at the interface through the spatially correlated activation of neighbouring defects. Emitter spectra further offer a direct readout of the local dielectric properties, unveiling increasing dielectric order under nanometre-scale confinement. Liquid-activated native hexagonal boron nitride defects bridge the gap between solid-state nanophotonics and nanofluidics, opening new avenues for nanoscale sensing and optofluidics.

Metastable 1T'-phase group VIB transition metal dichalcogenide crystals.

Metastable 1T'-phase transition metal dichalcogenides (1T'-TMDs) with semi-metallic natures have attracted increasing interest owing to their uniquely distorted structures and fascinating phase-dependent physicochemical properties. However, the synthesis of high-quality metastable 1T'-TMD crystals, especially for the group VIB TMDs, remains a challenge. Here, we report a general synthetic method for the large-scale preparation of metastable 1T'-phase group VIB TMDs, including WS2, WSe2, MoS2, MoSe2, WS2xSe2(1-x) and MoS2xSe2(1-x). We solve the crystal structures of 1T'-WS2, -WSe2, -MoS2 and -MoSe2 with single-crystal X-ray diffraction. The as-prepared 1T'-WS2 exhibits thickness-dependent intrinsic superconductivity, showing critical transition temperatures of 8.6 K for the thickness of 90.1 nm and 5.7 K for the single layer, which we attribute to the high intrinsic carrier concentration and the semi-metallic nature of 1T'-WS2. This synthesis method will allow a more systematic investigation of the intrinsic properties of metastable TMDs.

Preparation of CdSy Se1- y -MoS2 Heterostructures via Cation Exchange of Pre-Epitaxially Synthesized Cu2- χ Sy Se1- y -MoS2 for Photocatalytic Hydrogen Evolution.

Construction of 2D transition metal dichalcogenide (TMD)-based epitaxial heterostructures with different compositions is important for various promising applications, including electronics, photonics, and catalysis. However, the rational design and controlled synthesis of such kind of heterostructures still remain challenge, especially for those consisting of layered TMDs and other non-layered materials. Here, a facile one-pot, wet-chemical method is reported to synthesize Cu2- χ Sy Se1- y -MoS2 heterostructures in which two types of different epitaxial configurations, i.e., vertical and lateral epitaxies, coexist. The chalcogen ratio (S/Se) in Cu2- χ Sy Se1- y and the loading amount of MoS2 in the heterostructures can be tuned. Impressively, the obtained Cu2- χ Sy Se1- y -MoS2 heterostructures can be transformed to CdSy Se1- y -MoS2 without morphological change via cation exchange. As a proof-of-concept application, the obtained CdSy Se1- y -MoS2 heterostructures with controllable compositions are used as photocatalysts, exhibiting distinctive catalytic activities toward the photocatalytic hydrogen evolution under visible light irradiation. The method paves the way for the synthesis of different TMD-based lateral epitaxial heterostructures with unique properties for various applications.

Ag@MoS2 Core-Shell Heterostructure as SERS Platform to Reveal the Hydrogen Evolution Active Sites of Single-Layer MoS2.

Understanding the reaction mechanism for the catalytic process is essential to the rational design and synthesis of highly efficient catalysts. MoS2 has been reported to be an efficient catalyst toward the electrochemical hydrogen evolution reaction (HER), but it still lacks direct experimental evidence to reveal the mechanism for MoS2-catalyzed electrochemical HER process at the atomic level. In this work, we develop a wet-chemical synthetic method to prepare the single-layer MoS2-coated polyhedral Ag core-shell heterostructure (Ag@MoS2) with tunable sizes as efficient catalysts for the electrochemical HER. The Ag@MoS2 core-shell heterostructures are used as ideal platforms for the real-time surface-enhanced Raman spectroscopy (SERS) study owing to the strong electromagnetic field generated in the plasmonic Ag core. The in situ SERS results provide solid Raman spectroscopic evidence proving the S-H bonding formation on the MoS2 surface during the HER process, suggesting that the S atom of MoS2 is the catalytic active site for the electrochemical HER. It paves the way on the design and synthesis of heterostructures for exploring their catalytic mechanism at atomic level based on the in situ SERS measurement.

Quest for p-Type Two-Dimensional Semiconductors.

Two-dimensional (2D) semiconductors have demonstrated great potential in modern nanotechnologies across a variety of research fields, including (opto-)electronics, spintronics, and electro-/photocatalysis. Interestingly, the vast majority of 2D semiconductors, such as the widely explored transition-metal dichalcogenides, are n-type or ambipolar. The search for p-type 2D semiconductors in the past decade has succeeded in identifying only a few promising candidate materials. In this Perspective, we discuss various strategies to obtain p-type conduction in normally n-type or ambipolar 2D semiconductors and, more importantly, the direct synthesis of p-type 2D semiconductors such as black phosphorus, 2D tellurium, and, most recently, α-MnS.

In-Plane Anisotropic Properties of 1T'-MoS2 Layers.

Crystal phases play a key role in determining the physicochemical properties of a material. To date, many phases of transition metal dichalcogenides have been discovered, such as octahedral (1T), distorted octahedral (1T'), and trigonal prismatic (2H) phases. Among these, the 1T' phase offers unique properties and advantages in various applications. Moreover, the 1T' phase consists of unique zigzag chains of the transition metals, giving rise to interesting in-plane anisotropic properties. Herein, the in-plane optical and electrical anisotropies of metastable 1T'-MoS2 layers are investigated by the angle-resolved Raman spectroscopy and electrical measurements, respectively. The deconvolution of J1 and J2 peaks in the angle-resolved Raman spectra is a key characteristic of high-quality 1T'-MoS2 crystal. Moreover, it is found that its electrocatalytic performance may be affected by the crystal orientation of anisotropic material due to the anisotropic charge transport.

Preparation of 1T'-Phase ReS2 xSe2(1- x) ( x = 0-1) Nanodots for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction.

As a source of clean energy, a reliable hydrogen evolution reaction (HER) requires robust and highly efficient catalysts. Here, by combining chemical vapor transport and Li-intercalation, we have prepared a series of 1T'-phase ReS2 xSe2(1- x) ( x = 0-1) nanodots to achieve high-performance HER in acid medium. Among them, the 1T'-phase ReSSe nanodot exhibits the highest hydrogen evolution activity, with a Tafel slope of 50.1 mV dec-1 and a low overpotential of 84 mV at current density of 10 mA cm-2. The excellent hydrogen evolution activity is attributed to the optimal hydrogen absorption energy of the active site induced by the asymmetric S vacancy in the highly asymmetric 1T' crystal structure.

High phase-purity 1T'-MoS2- and 1T'-MoSe2-layered crystals.

Phase control plays an important role in the precise synthesis of inorganic materials, as the phase structure has a profound influence on properties such as conductivity and chemical stability. Phase-controlled preparation has been challenging for the metallic-phase group-VI transition metal dichalcogenides (the transition metals are Mo and W, and the chalcogens are S, Se and Te), which show better performance in electrocatalysis than their semiconducting counterparts. Here, we report the large-scale preparation of micrometre-sized metallic-phase 1T'-MoX2 (X = S, Se)-layered bulk crystals in high purity. We reveal that 1T'-MoS2 crystals feature a distorted octahedral coordination structure and are convertible to 2H-MoS2 following thermal annealing or laser irradiation. Electrochemical measurements show that the basal plane of 1T'-MoS2 is much more active than that of 2H-MoS2 for the electrocatalytic hydrogen evolution reaction in an acidic medium.

Quasi-Stem Cells Derived from Human Somatic Cells by Chemically Modified Carbon Nanotubes.

Surface modification of micro- and nanotopography was employed to alter the surface properties of scaffolds for controlling cell attachment, proliferation, and differentiation. This study reports a method for generating multinucleated colonies as evidenced by spherical colony formation through nanotopography-induced expression of reprogramming factors in human dermal fibroblasts. Colony formation was achieved by subjecting the cells to specific environments such as culturing with single-walled carbon nanotubes and poly-l-lysine (PLL-SWCNTs). We obtained encouraging results showing that PLL-SWCNT treatment transformed fibroblast cells, and the transformed cells expressed the pluripotency-associated factors OCT4, NANOG, and SOX2 in addition to TRA-1-60 and SSEA-4, which are characteristic stem cell markers. Downregulation of lamin A/C, HDAC1, HDAC6, Bcl2, cytochrome c, p-FAK, p-ERK, and p-JNK and upregulation of H3K4me3 and p-p38 were confirmed in the generated colonies, indicating reprogramming of cells. This protocol increases the possibility of successfully reprogramming somatic cells into induced pluripotent stem cells (iPSCs), thereby overcoming the difficulties in iPSC generation such as genetic mutations, carcinogenesis, and undetermined risk factors.

Recent Advances in Ultrathin Two-Dimensional Nanomaterials.

Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocatalysis, batteries, supercapacitors, solar cells, photocatalysis, and sensing platforms. Finally, the challenges and outlooks in this promising field are featured on the basis of its current development.

Improved Reversibility of Fe3+ /Fe4+ Redox Couple in Sodium Super Ion Conductor Type Na3 Fe2 (PO4 )3 for Sodium-Ion Batteries.

The methodology employed here utilizes the sodium super ion conductor type sodium iron phosphate wrapped with conducting carbon network to generate a stable Fe3+ /Fe4+ redox couple, thereby exhibiting higher operating voltage and energy density of sodium-ion batteries. This new class of sodium iron phosphate wrapped by carbon also displays a cycling stability with >96% capacity retention after 200 cycles.

In Situ Fabrication of Nano Transistors by Selective Deposition of a Gate Dielectric around Carbon Nanotubes.

The CNT-SiO2 core-shell structure is particularly appealing because the insulating SiO2 layer wraps around the CNTs, functioning as a gate dielectric. However, it is still a challenge to expose both end-caps of the structure for enabling them to serve as electrodes, which additionally requires complicated postprocesses. Here, we present a unique CNTs-SiO2 core-shell structure where both ends are uncovered with SiO2 in a "peeled-wire" structure. In this structure, SiO2 particles partially encapsulate the CNTs during the synthesis, resulting in both end-caps of the nanotube being self-exposed and electrically conductive. The field-effect transistor build-up with this structure exhibits p-type characteristics with a linear conductance behavior on Id-Vd output performance. This approach for making self-formed electrodes in the CNT-SiO2 core-shell structure provides a simple and efficient way for applying them to future nanodevices in terms of process simplicity and cost effectiveness.

Fabrication of gold nanoflowers by template-assisted electrodeposition.

Gold (Au) nanoflowers have been fabricated using anodic aluminum oxide (AAO) templates assisted electrochemical deposition on the Au film, in which the templates were coated by poly (dimethyl siloxane) (PDMS). PDMS is a viscous, soft material which helps the AAO template to stick to the Au film and assists in the formation of flower-like nanostructures. First, Au nanoplates grew in one-dimensional (1D) pores of the AAO template and uniformly distributed on the Au film; afterwards, the nanoplates continued to grow three-dimensionally because the contracted PDMS provided more space and further formed flower-like shape. The Au nanostructures were characterized by field emission scanning electron microscopy (FE-SEM) as well as energy-dispersive spectroscopy (EDS). Enhanced fluorescence was observably detected along the change of the surface morphology and the nanoflowers exhibited a higher intensity than other Au nanostructures.

Preparation of hierarchically aligned carbon nanotube films using the Langmuir-Blodgett technique.

Hierarchically-aligned single-walled carbon nanotube (SWNT) films over large areas were fabricated by using Langmuir-Blodgett (LB) technique. Thiophenyl-modified SWNTs spreading solution in chloroform was prepared through amidation reaction of oxidized SWNTs. The resulting SWNTs were found to form stable colloidal suspensions in organic solvents, such as chloroform, which is a suitable solvent for the LB application. The compression of the thiophenyl-modified SWNTs spread onto the water surface of an LB trough leading to a uniform SWNT Langmuir monolayer, where SWNTs were aligned parallel to the trough barrier. Optical anisotropy of SWNTs LB films on quartz substrate was confirmed by polarized UV-Vis/NIR spectroscopic measurement. Moreover, the electrical conductivity of the resulting SWNT films, which were parallel to the tube axis, was found to be approximately 15 times higher than those that were perpendicular to the axis, reflecting anisotropic electrical properties due to the uniaxial alignment of individual SWNT bundles.