Two-dimensional molybdenum disulfide (2D MoS2) is considered as a promising candidate for many applications due to its unique structure and properties. However, the controllable synthesis of large-scale and high-quality 2D 1T-phase MoS2 is still a challenge. Herein, we present the scalable and controllable synthesis of 2D MoS2 from 2H to 1T@2H phase by using K2SO4 salt as a simultaneous high-temperature sulfur source and template. The as-synthesized 1T@2H-2D MoS2 exhibits a high yield and can be easily assembled into freestanding electrode with high specific capacitance of 434 F/g at a scan rate of 1 mV/s in LiClO4 ethylene carbonate/dimethyl carbonate (EC/DMC). Moreover, various single-crystal 2D transition metal sulfides (WS2, PbS, MnS and Ni9S8) and 2D S-doped carbon can be synthesized using this method. We believe that this study may provide a new sight for scalable and controllable synthesis of other 2D materials beyond 2D MoS2.
Chemical vapor deposition (CVD) is the most efficient method to grow large-area two dimensional (2D) transition metal dichiacogenides (TMDCs) in high quality. Monolayer molybdenum disulfide (MoS2) and seed-assistant are the mostly selected 2D TMDC and growth strategy for such CVD processes, respectively. Though the advantages of seed catalysts in facilitating the nucleation, achieving higher yield and better repeatability, as well as their effects on the morphologies of as-grown MoS2 have been studied, the influence of seeding promoters on both optical and electrical properties of as-grown monolayer MoS2 is not known comprehensively, which is indeed critical for understanding fundamental physics and developing practical application of such emerging 2D semiconductors. In this report, we systematically investigated the effect of different seeding promoters on the properties of CVD-grown monolayer MoS2. It is found that different seed molecules lead to different impacts on the optical and electrical properties of as-grown monolayer MoS2. Among three different seed catalysts (perylene-3,4,9,10-tetracarboxylic acid tetrapotassium salt (PTAS), copper phthalocyanine (CuPc), and crystal violet (CV)), PTAS performs better in obtaining large area monolayer MoS2 with good optical quality and high electrical mobility than the other two. Our work gives a guide for modifying the properties of as-grown monolayer MoS2 and other 2D transition metal dichalcogenides in seeding promoters-assisted synthesis process.
Potassium-ion batteries are regarded as the low-cost alternative to lithium-ion batteries. However, their development is hampered by the lack of suitable electrode materials. In this work, we demonstrate that MoS2 with expanded interlayers represents a promising candidate for the electrochemical storage of potassium ions. Hierarchical interlayer-expanded MoS2 assemblies supported on carbon nanotubes are prepared via a straightforward solution method. The increased interlayer spacing not only enables the better accommodation of foreign ions, but also lowers the diffusion energy barrier and improves diffusion kinetics of ions. When investigated as the anode material of potassium ion batteries, our interlayer-expanded MoS2 assemblies exhibit an excellent electrochemical performance with large capacity (up to ∼ 520 mAhg−1), good rate capability (∼ 310 mAhg−1 at 1,000 mAg−1) and impressive cycling stability, superior to most competitors.
DNA-based nanofabrication of inorganic nanostructures has potential application in electronics, catalysis, and plasmonics. Previous DNA metallization has generated conductive DNA-assembled nanostructures; however, the use of semiconductors and the development of well-connected nanoscale metal—semiconductor junctions on DNA nanostructures are still at an early stage. Herein, we report the first fabrication of multiple electrically connected metal—semiconductor junctions on individual DNA origami by location-specific binding of gold and tellurium nanorods. Nanorod attachment to DNA origami was via DNA hybridization for Au and by electrostatic interaction for Te. Electroless gold plating was used to create nanoscale metal—semiconductor interfaces by filling the gaps between Au and Te nanorods. Two-point electrical characterization indicated that the Au—Te—Au junctions were electrically connected, with current—voltage properties consistent with a Schottky junction. DNA-based nanofabrication of metal—semiconductor junctions opens up potential opportunities in nanoelectronics, demonstrating the power of this bottom-up approach.
A reproducible synthetic strategy was developed for facile large-scale (200 mg) synthesis of surface silanized magnetite (Fe3O4) nanoparticles (NPs) for biological applications. After further coupling a phosphate-specific affinity ligand, these functionalized magnetic NPs were used for the highly specific enrichment of phosphoproteins from a complex biological mixture. Moreover, correlating the surface silane density of the silanized magnetite NPs to their resultant enrichment performance established a simple and reliable quality assurance control to ensure reproducible synthesis of these NPs routinely in large scale and optimal phosphoprotein enrichment performance from batch-to-batch. Furthermore, by successful exploitation of a top-down phosphoproteomics strategy that integrates this high throughput nanoproteomics platform with online liquid chromatography (LC) and tandem mass spectrometry (MS/MS), we were able to specifically enrich, identify, and characterize endogenous phosphoproteins from highly complex human cardiac tissue homogenate. This nanoproteomics platform possesses a unique combination of scalability, specificity, reproducibility, and efficiency for the capture and enrichment of low abundance proteins in general, thereby enabling downstream proteomics applications.
Atomically thin transition metal dichalcogenides (TMDs) have distinct opto-electronic properties including enhanced luminescence and high on-off current ratios, which can be further modulated by making more complex TMD heterostructures. However, resolution limits of conventional optical methods do not allow for direct nanoscale optical-structural correlation measurements in these materials, particularly of buried interfaces in TMD heterostructures. Here we use, for the first time, electron beam induced cathodoluminescence in a scanning transmission electron microscope (CL-STEM) to measure optical properties of monolayer TMDs (WS2, MoS2 and WSSe alloy) encapsulated between layers of hBN. We observe dark areas resulting from localized (~ 100 nm) imperfect interfaces and monolayer folding, which shows that the intimate contact between layers in this application-relevant heterostructure is required for proper inter layer coupling. We also realize a suitable imaging method that minimizes electron-beam induced changes and provides measurement of intrinsic properties. To overcome the limitation of small electron interaction volume in TMD monolayer (and hence low photon yield), we find that encapsulation of TMD monolayers with hBN and subsequent annealing is important. CL-STEM offers to be a powerful method to directly measure structure-optical correspondence in lateral or vertical heterostructures and alloys.
Two-dimensional (2D) MoS2 with appealing physical properties is a promising candidate for next-generation electronic and optoelectronic devices, where the ultrathin MoS2 is usually laid on or gated by a dielectric oxide layer. The oxide/MoS2 interfaces widely existing in these devices have significant impacts on the carrier transport of the MoS2 channel by diverse interface interactions. Artificial design of the oxide/MoS2 interfaces would provide an effective way to break through the performance limit of the 2D devices but has yet been well explored. Here, we report a high-performance MoS2-based phototransistor with an enhanced photoresponse by interfacing few-layer MoS2 with an ultrathin TiO2 layer. The TiO2 is deposited on MoS2 through the oxidation of an e-beam-evaporated ultrathin Ti layer. Upon a visible-light illumination, the fabricated TiO2/MoS2 phototransistor exhibits a responsivity of up to 2,199 A/W at a gate voltage of 60 V and a detectivity of up to 1.67 × 1013 Jones at a zero-gate voltage under a power density of 23.2 µW/mm2. These values are 4.0 and 4.2 times those of the pure MoS2 phototransistor. The significantly enhanced photoresponse of TiO2/MoS2 device can be attributed to both interface charge transfer and photogating effects. Our results not only provide valuable insights into the interactions at TiO2/MoS2 interface, but also may inspire new approach to develop other novel optoelectronic devices based on 2D layered materials.
Lanthanide-based luminescent anti-counterfeiting materials are widely used in various kinds of products. However, the emission color of traditional lanthanide-based luminescent materials usually remains nearly unaltered upon different excitation lights, which may only work for single-level anti-counterfeiting. Herein, the NaYbF4:2%Er@NaYF4 core/shell nanoplates (NPs) with “chameleon-like” optical behavior are developed. These NPs display single-band red or green downshifting (DS) emission upon excitation at 377 or 490 nm, respectively. Upon 980 nm excitation, the color of upconversion (UC) emission can be finely tuned from green to yellow, and to red with increasing the excitation power density from 0.1 to 4.0 W/cm2. The proposed materials readily integrate the advantages of excitation wavelength-dependent DS single-band emissions and sensitive excitation power-dependent UC multicolor emissions in one and the same material, which has never been reported before. Particularly, the proposed NPs exhibit excellent performance as security labels on trademark tag and security ink on painting, thus revealing the great potential of these lanthanide-doped fluoride NPs in multilevel anti-counterfeiting applications.
Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm2 in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr2O3. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.
As nanomedicine-based clinical strategies have continued to develop, the possibility of combining chemotherapy and singlet oxygen-dependent photodynamic therapy (PDT) to treat pancreatic cancer (PaC) has emerged as a viable therapeutic modality. The efficacy of such an approach, however, is likely to be constrained by the mechanisms of drug release and tumor oxygen levels. In the present study, we developed an Fe(III)-complexed porous coordination network (PCN) which we then used to encapsulate PTX (PCN-Fe(III)-PTX) nanoparticles (NPs) in order to treat PaC via a combination of chemotherapy and PDT. The resultant NPs were able to release drug in response to both laser irradiation and pH changes to promote drug accumulation within tumors. Furthermore, through a Fe(III)-based Fenton-like reaction these NPs were able to convert H2O2 in the tumor site to O2, thereby regulating local hypoxic conditions and enhancing the efficacy of PDT approaches. Also these NPs were suitable for use as a T1-MRI weighted contrast agent, making them viable for monitoring therapeutic efficacy upon treatment. Our results in both cell line and animal models of PaC suggest that these NPs represent an ideal agent for mediating effective MRI-guided chemotherapy-PDT, giving them great promise for the clinical treatment of PaC.
Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have emerged as perfect platforms for developing applications in nano-electronics, catalysis, energy storage and environmental-related fields due to their superior properties. However, the low-cost, batch production of high-quality 2D TMDCs remains a huge challenge with the existing synthetic strategies. Herein, we present a scalable chemical vapor deposition (CVD) approach for the batch production of high-quality MoS2 nanosheet powders, by using naturally abundant, water-soluble and recyclable NaCl crystal powders as templates. The high-quality MoS2 nanosheets powders are achieved by a facile water dissolution-filtration process, by virtue of the excellent dispersibility of the as-grown products in water. The internal mechanism for the scalable synthesis strategy is explored. The applications of the MoS2 nanosheets powders are also demonstrated as catalysts or adsorbents in hydrogen evolution reaction (HER) and organic dyes adsorption, respectively. This work should hereby pave ways for the mass production and application of powdery TMDCs in energetic and environmental related fields.
Anisotropic two-dimensional (2D) materials exhibit lattice-orientation dependent optical and electrical properties. Carriers doping of such materials has been used to modulate their energy band structures for opto-electronic applications. Herein, we show that by stacking monolayer rhenium disulfide (ReS2) on a flat gold film, the electrons doping in ReS2 can affect the in-plane anisotropic Raman enhancement of molecules adsorbed on ReS2. The change of enhancement factor and the degree of anisotropy in enhancement with layer number are sensitively dependent on the doping level of ReS2 by gold, which is further confirmed by Kelvin probe force microscopy (KPFM) measurements. These findings could open an avenue for probing anisotropic electronic interactions between molecules and 2D materials with low symmetry using Raman enhancement effect.
A three-dimensional copper metal—organic framework with the rare chabazite (CHA) topology namely FJI-Y11 has been constructed with flexibly carboxylic ligand 5,5′-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic acid (H4L). FJI-Y11 exhibits high water stability with the pH range from 2 to 12 at temperature as high as 373 K. Importantly, FJI-Y11 also shows high efficiency of hydrogen isotope separation using dynamic column breakthrough experiments under atmospheric pressure at 77 K. Attributed to its excellent structural stability, FJI-Y11 possesses good regenerated performance and maintains high separation efficiency after three cycles of breakthrough experiments.
Nanoparticles (NPs) which are innovation and research focus in drug delivery systems, still have some disadvantages limiting its application in clinical use, such as short circulation time, recognition and clearance by reticuloendothelial system (RES) and passive targeting in certain organs. However, the recent combination of natural components and nanotechnology has offered new solutions to address these problems. A novel biomimetic platform consisting of nanoparticle core and membrane shell, such as cell membrane, exosome or vesicle vastly improves properties of nanoparticles. These coated nanoparticles can replicate the unique functions of the membrane, such as prolonged blood circulation, active targeting capability and enhanced internalization. In this review, we focus on the newest development of biological-camouflaged nanoparticles and mainly introduce its application related to cancer therapy and toll-like receptor.
Two-dimensional (2D) nanomaterials have attracted a great deal of attention since the discovery of graphene in 2004, due to their intriguing physicochemical properties and wide-ranging applications in catalysis, energy-related devices, electronics and optoelectronics. To maximize the potential of 2D nanomaterials for their technological applications, controlled assembly of 2D nanobulding blocks into integrated systems is critically needed. This mini review summarizes the reported strategies of 2D materials-based assembly into integrated functional nanostructures, from in-situ assembly method to post-synthesis assembly. The applications of 2D assembled integrated structures are also covered, especially in the areas of energy, electronics and sensing, and we conclude with discussion on the remaining challenges and potential directions in this emerging field.
Two-dimensional (2D) oxide can be continuously produced by bubbling oxygen into liquid metals and the harvesting of these oxide relies on the proper choice of dispersion solvents. The mass-production of ligand-free 2D materials from high melting-point metals will not be possible if the limited stability of the traditional dispersion solvents is not circumvented. Herein, liquid tin was used for the first time in the bubbling protocol and 2D tin oxide was obtained in molten salts. The nanosheets were studied with combined microscopic and spectroscopic techniques, and high-density grain boundaries was identified between the sub-5-nm nano-crystallites in the nanosheets. It gives rise to the high performance in electrocatalytic CO2 reduction reaction. Density-functional-theory based calculation was applied to achieve a deeper understanding of the relationship between the activity, selectivity, and the grain-boundary features. The molten-salt based protocol could be explored for the synthesis of a library of functional 2D oxides.
Colloidal nanoparticles with anisotropic architectures have attracted a variety of interest and attention due to different physical and chemical properties compared with the isotropic counterparts, making them promising candidates in many fundamental studies and practical applications. Particularly, carbon and silica-based anisotropic nanoparticles can be one stand out by combing both intrinsic merits of carbons and silica, such as structural stability, biocompatibility, large surface area, and ease of functionalization with the anisotropic structural complexity. In this review, we aim to provide an updated summary of the research related to the anisotropic carbon and silica-based nanostructures, covering both their synthesis and applications.
