ABSTRACT: Since the discovery of graphene, the quest for two-dimensional (2D) materials has intensified greatly. Recently, a new family of 2D transition metal carbides and carbonitrides (MXenes) was discovered that is both conducting and hydrophilic, an uncommon combination. To date MXenes have been produced as powders, flakes, and colloidal solutions. Herein, we report on the fabrication of ?1 × 1 cm(2) Ti3C2 films by selective etching of Al, from sputter-deposited epitaxial Ti3AlC2 films, in aqueous HF or NH4HF2. Films that were about 19 nm thick, etched with NH4HF2, transmit ?90% of the light in the visible-to-infrared range and exhibit metallic conductivity down to ?100 K. Below 100 K, the films' resistivity increases with decreasing temperature and they exhibit negative magnetoresistance-both observations consistent with a weak localization phenomenon characteristic of many 2D defective solids. This advance opens the door for the use of MXenes in electronic, photonic, and sensing applications.
Project description:Abstract 2D transition metal carbides, nitrides, and carbonitrides called MXenes show outstanding performance in many applications due to their superior physical and chemical properties. Herein, a ZnO–MXene mixture with different contents of Ti3C2 is applied as electron transport layers (ETLs) and the influence of the Ti3C2 MXene in all?inorganic metal halide perovskite nanocrystal light?emitting diodes (perovskite NC LEDs) is explored. The addition of Ti3C2 makes more balanced charge carrier transport in LEDs by changing the energy level structure and electron mobility of ETL. Moreover, lower surface roughness is obtained for the ETL, thus guaranteeing uniform distribution of the perovskite NCs layer and further reducing leakage current. As a result, a 17.4% external quantum efficiency (EQE) with low efficiency roll?off is achieved with 10% Ti3C2, which is a 22.5% improvement compared to LEDs without Ti3C2. Adding an appropriate amount of Ti3C2 into the ZnO electron transport layer (ETL) to change the energy level structure and electron mobility of the ETL and further make the carrier transport balanced is explored. The ZnO/TiC ETL?based red emitting perovskite nanocrystals light?emitting diodes exhibit an external quantum efficiency of 17.4%.
Project description:Current trends in the field of MXenes emphasize the importance of controlling their surface features for successful application in biotechnological areas. The ability to stabilize the surface properties of MXenes has been demonstrated here through surface charge engineering. It was thus determined how changing the surface charges of two-dimensional (2D) Ti3C2 MXene phase flakes using cationic polymeric poly-L-lysine (PLL) molecules affects the colloidal and biological properties of the resulting hybrid 2D nanomaterial. Electrostatic adsorption of PLL on the surface of delaminated 2D Ti3C2 flakes occurs efficiently, leads to changing an MXene's negative surface charge toward a positive value, which can also be effectively managed through pH changes. Analysis of bioactive properties revealed additional antibacterial functionality of the developed 2D Ti3C2/PLL MXene flakes concerning Escherichia. coli Gram-negative bacteria cells. A reduction of two orders of magnitude of viable cells was achieved at a concentration of 200 mg L-1. The in vitro analysis also showed lowered toxicity in the concentration range up to 375 mg L-1. The presented study demonstrates a feasible approach to control surface properties of 2D Ti3C2 MXene flakes through surface charge engineering which was also verified in vitro for usage in biotechnology or nanomedicine applications.
Project description:The residual of malignant tumor cells and lack of bone-tissue integration are the two critical concerns of bone-tumor recurrence and surgical failure. In this work, the rational integration of 2D Ti3C2 MXene is reported with 3D-printing bioactive glass (BG) scaffolds for achieving concurrent bone-tumor killing by photonic hyperthermia and bone-tissue regeneration by bioactive scaffolds. The designed composite scaffolds take the unique feature of high photothermal conversion of integrated 2D Ti3C2 MXene for inducing bone-tumor ablation by near infrared-triggered photothermal hyperthermia, which has achieved the complete tumor eradication on in vivo bone-tumor xenografts. Importantly, the rational integration of 2D Ti3C2 MXene is demonstrated to efficiently accelerate the in vivo growth of newborn bone tissue of the composite BG scaffolds. The dual functionality of bone-tumor killing and bone-tissue regeneration makes these Ti3C2 MXene-integrated composite scaffolds highly promising for the treatment of bone tumors, which also substantially broadens the biomedical applications of 2D MXenes in tissue engineering, especially on the treatment of bone tumors.
Project description:Mn+1AXn phases are a large family of compounds that have been limited, so far, to carbides and nitrides. Here we report the prediction of a compound, Ti2InB2, a stable boron-based ternary phase in the Ti-In-B system, using a computational structure search strategy. This predicted Ti2InB2 compound is successfully synthesized using a solid-state reaction route and its space group is confirmed as P[Formula: see text]m2 (No. 187), which is in fact a hexagonal subgroup of P63/mmc (No. 194), the symmetry group of conventional Mn+1AXn phases. Moreover, a strategy for the synthesis of MXenes from Mn+1AXn phases is applied, and a layered boride, TiB, is obtained by the removal of the indium layer through dealloying of the parent Ti2InB2 at high temperature under a high vacuum. We theoretically demonstrate that the TiB single layer exhibits superior potential as an anode material for Li/Na ion batteries than conventional carbide MXenes such as Ti3C2.
Project description:Ultrathin transition metal carbides with high capacity, high surface area, and high conductivity are a promising family of materials for applications from energy storage to catalysis. However, large-scale, cost-effective, and precursor-free methods to prepare ultrathin carbides are lacking. Here, we demonstrate a direct pattern method to manufacture ultrathin carbides (MoCx, WCx, and CoCx) on versatile substrates using a CO2 laser. The laser-sculptured polycrystalline carbides (macroporous, ~10-20 nm wall thickness, ~10 nm crystallinity) show high energy storage capability, hierarchical porous structure, and higher thermal resilience than MXenes and other laser-ablated carbon materials. A flexible supercapacitor made of MoCx demonstrates a wide temperature range (-50 to 300 °C). Furthermore, the sculptured microstructures endow the carbide network with enhanced visible light absorption, providing high solar energy harvesting efficiency (~72 %) for steam generation. The laser-based, scalable, resilient, and low-cost manufacturing process presents an approach for construction of carbides and their subsequent applications.
Project description:Owing to their high robustness and conductivity, 2D transition metal carbides and nitrides known as MXenes are considered as a promising material class for electrochemical catalysis, energy conversion, and storage applications. Nevertheless, conventional hazardous fluoride-based synthesis routes and the intense intralayer bonding restrict the development of MXenes. Herein, a fluoride-free, facile, and rapid method for synthesizing self-assembled 1D architecture from an MXene-based compound is reported. The MXene nanowire (NW) not only provides a robust connection to the flexible substrate but also effectively increases the electrochemically active surface area. The kinetics-favorable structure yields a boosted performance for the hydrogen/oxygen evolution reaction and the intake of the zinc ion. The 1D NW based on MXene compound maintains high stability in a quite low overpotential of 236 mV for 24 h without detachment from the substrate and manifests an exceptional high-power density of 420 W kg-1 over 150 cycles as a flexible aqueous zinc ion battery. This work paves a novel and non-toxic synthesis method for the 1D nanofiber structure from MXene composition and demonstrates its multifunctional applications for energy conversion and storage.
Project description:ZnSnxGe1-xN2 alloys are chemically miscible semiconductor compounds with potential application as earth-abundant alternatives to InxGa1-xN. Preparation of ZnSnxGe1-xN2 thin-films by reactive RF sputter deposition yield low-mobility, nanocrystalline films. In contrast, the growth of ZnSnxGe1-xN2 films by molecular-beam epitaxy (MBE) on c-plane sapphire and GaN templates is described herein. Epitaxial films exhibited 3D growth on sapphire and 2D single-crystal quality on GaN, exhibiting substantial improvements in epitaxy and crystallinity relative to nanocrystalline sputtered films. Films on sapphire were n-type with electronic mobilities as high as 18?cm2?V-1 s-1, an order of magnitude greater than the 2?cm2?V-1 s-1 average mobility observed in this work for sputtered films. Mobility differences potentially arise from strain or surface effects originating from growth techniques, or from differences in film thicknesses. In general, MBE growth has provided desired improvements in electronic mobility, epitaxy, and crystal quality that provide encouragement for the continued study of ZnSnxGe1-xN2 alloys.
Project description:A recently created class of inorganic 2D materials, MXenes, has become a subject of intensive research. Reducing their dimensionality from 2D to 0D quantum dots (QDs) could result in extremely useful properties and functions. However, this type of research is scarce, and the reported Ti3C2 MXene QDs (MQDs) have only shown blue fluorescence emission. This work demonstrates a facile, high-output method for preparing bright white emitting Ti3C2 MQDs. The resulting product is two layers thick with a lateral dimension of 13.1 nm. Importantly, the as prepared Ti3C2 MQDs present strong two-photon white fluorescence. Their fluorescence under high pressure is also investigated and it is found that the white emission is very stable and the pressure makes it possible to change from cool white emission to warm white emission. Hybrid nanocomposites are then fabricated by polymerizing Ti3C2 MQDs in polydimethylsiloxane (PDMS) solution, and the bright white emitting hybrid materials in white light-emitting diodes are used. This work provides a facile and general approach to modulate various nanoscale MXene materials, and could further aid the wide development of applications for MXene materials in various optical-related fields.
Project description:Developing strategies for atomic-scale controlled synthesis of new two-dimensional (2D) functional materials will directly impact their applications. Here, using in situ aberration-corrected scanning transmission electron microscopy, we obtain direct insight into the homoepitaxial Frank-van der Merwe atomic layer growth mechanism of TiC single adlayers synthesized on surfaces of Ti3C2 MXene substrates with the substrate being the source material. Activated by thermal exposure and electron-beam irradiation, hexagonal TiC single adlayers form on defunctionalized surfaces of Ti3C2 MXene at temperatures above 500?°C, generating new 2D materials Ti4C3 and Ti5C4. The growth mechanism for a single TiC adlayer and the energies that govern atom migration and diffusion are elucidated by comprehensive density functional theory and force-bias Monte Carlo/molecular dynamics simulations. This work could lead to the development of bottom-up synthesis methods using substrates terminated with similar hexagonal-metal surfaces, for controllable synthesis of larger-scale and higher quality single-layer transition metal carbides.
Project description:The exploration of two-dimensional solids is an active area of materials discovery. Research in this area has given us structures spanning graphene to dichalcogenides, and more recently 2D transition metal carbides (MXenes). One of the challenges now is to master ordering within the atomic sheets. Herein, we present a top-down, high-yield, facile route for the controlled introduction of ordered divacancies in MXenes. By designing a parent 3D atomic laminate, (Mo2/3Sc1/3)2AlC, with in-plane chemical ordering, and by selectively etching the Al and Sc atoms, we show evidence for 2D Mo1.33C sheets with ordered metal divacancies and high electrical conductivities. At ?1,100?F?cm-3, this 2D material exhibits a 65% higher volumetric capacitance than its counterpart, Mo2C, with no vacancies, and one of the highest volumetric capacitance values ever reported, to the best of our knowledge. This structural design on the atomic scale may alter and expand the concept of property-tailoring of 2D materials.