Oxidation of Molybdenum-Based Single-Metallic/bimetallic Carbide MXenes in Aqueous Suspensions: Mechanistic Insights.

Molybdenum carbide MXenes have garnered considerable attention in electronics, energy storage, and catalysis. However, they are prone to oxidative degradation, but the associated mechanisms have not been systematically explored. Therefore, the oxidation mechanisms of Mo-based single-metallic/bimetallic carbide MXenes including Mo2CTx, Mo2TiC2Tx, and Mo2Ti2C3Tx in aqueous suspensions were investigated for the first time in this study. Similar to Ti3C2Tx MXene, Mo-based MXenes were found to undergo oxidative degradation in their aqueous dispersions, leading to the disruption of their crystal structure and subsequent loss of optical and electronic properties. Notably, the Mo2CTx MXene deviated from this typical oxidation behavior as it produced an amorphous product with Mo ions instead of highly crystalline Mo-oxides during oxidation. Similarly, the Mo2TiC2Tx and Mo2Ti2C3Tx MXenes did not yield crystalline Mo-oxides; instead, they produced highly crystalline anatase TiO2 and a Mo-ion-containing amorphous product simultaneously. Furthermore, high-temperature annealing of the oxidized Mo2CTx MXene powder at 800 °C transformed the amorphous Mo-containing product into highly crystalline MoO2 crystals. These findings highlight the unconventional oxidation behavior of Mo-based MXenes, which suggests that the formation of crystalline Mo-based oxides requires a higher activation energy during oxidation than that of TiO2. The unique oxidative pathway reported herein can help elucidate the oxidation mechanisms of Mo-based MXene dispersions and their products. The insights from this study can pave the way for fundamental studies in academia as well as broaden the applications of Mo-based MXenes in various industries.

Ultrahigh Nonlinear Responses from MXene Plasmons in the Short-Wave Infrared Range.

Surface plasmons in 2D materials such as graphene exhibit exceptional field confinement. However, the low electron density of majority of 2D materials, which are semiconductors or semimetals, has limited their plasmons to mid-wave or long-wave infrared regime. This study demonstrates that a 2D Ti3C2Tx MXene with high electron density can not only support strong plasmon confinement with an acoustic plasmon mode in the short-wave infrared region, but also provide ultrahigh nonlinear responses. The acoustic MXene plasmons (AMPs) in the MXene (Ti3C2Tx)-insulator (SiO2)-metal (Au) nanostructure generate in the 1.5-6.0 µm wavelength range, exhibiting a two orders of magnitude reduction in wavelength compared to wavelength in free space. Furthermore, AMP resonators with patterned Au rods exhibit a record-high nonlinear absorption coefficient of 1.37 × 10-2 m W-1 at wavelength of 1.56 µm, ≈3 orders of magnitude greater than the highest value recorded for other 2D materials. These results indicate that MXenes can overcome fundamental plasmon wavelength limitations of previously studied 2D materials, providing groundbreaking opportunities in nonlinear optical applications, including all-optical processing and ultrafast optical switching.

Asymmetric Laser Field Interaction with MXene Coated on the Side Surface of Optical Fibers for Ultrafast Nonlinear Switches.

In recent years, there has been significant interest in researching ultrafast nonlinear optical phenomena involving light-matter interactions in two-dimensional (2D) materials, owing to their potential applications in optics and photonics. MXene, a recently developed 2D material, has garnered considerable attention due to its graphene-like properties and highly tunable electronic/optical characteristics. Herein, we demonstrate ultrafast all-optical switches based on four-wave-mixing (FWM) utilizing the nonlinear optical property of MXene Ti3C2Tx. In order to realize the device, we deposited multilayered Ti3C2Tx in the form of a supernatant solution onto the polished surface of a side-polished optical fiber, enabling the interaction of Ti3C2Tx with the asymmetric evanescent field of the incident input. We systematically characterized the nonlinear optical responses derived from the Ti3C2Tx layers. The fabricated device exhibits notable performance metrics, an enhancement of the extinction ratio, and a conversion efficiency of the newly generated signal, displaying 5.3 and 5.2 dB, respectively. Additionally, the device operates at high modulation frequencies, reaching up to 20 GHz, and demonstrates high-resolution detuning with channel distances of up to 15 nm. Our findings highlight the potential of MXene-based materials for ultrafast optical data management systems.

Tailoring Built-In Electric Field in a Self-Assembled Zeolitic Imidazolate Framework/MXene Nanocomposites for Microwave Absorption.

Heterointerface engineering, which plays a pivotal role in developing advanced microwave-absorbing materials, is employed to design zeolitic imidazolate framework (ZIF)-MXene nanocomposites. The ZIF-MXene composites are prepared by electrostatic self-assembly of negatively charged titanium carbide MXene flakes and positively charged Co-containing ZIF nanomaterials. This approach effectively creates abundant Mott-Schottky heterointerfaces exhibiting a robust built-in electric field (BIEF) effect, as evidenced by experimental and theoretical analyses, leading to a notable attenuation of electromagnetic energy. Systematic manipulation of the BIEF-exhibiting heterointerface, achieved through topological modulation of the ZIF, proficiently alters charge separation, facilitates electron migration, and ultimately enhances polarization relaxation loss, resulting in exceptional electromagnetic wave absorption performance (reflection loss RLmin = -47.35 dB and effective absorption bandwidth fE = 6.32 GHz). The present study demonstrates an innovative model system for elucidating the interfacial polarization mechanisms and pioneers a novel approach to developing functional materials with electromagnetic characteristics through spatial charge engineering.

Effect of Substitutional Oxygen on Properties of Ti3 C2 Tx MXene Produced Using Recycled TiO2 Source.

MXenes are an emerging class of 2D materials with unique properties including metallic conductivity, mechanical flexibility, and surface tunability, which ensure their utility for diverse applications. However, the synthesis of MXenes with high crystallinity and atomic stoichiometry in a low-cost process is still challenging because of the difficulty in controlling the oxygen substitute in the precursors and final products of MXenes, which limits their academic understanding and practical applications. Here, a novel cost-effective method is reported to synthesize a highly crystalline and stoichiometric Ti3 C2 Tx MXene with minimum substitutional oxygen impurities by controlling the amount of excess carbon and time of high-energy milling in carbothermal reduction of recycled TiO2 source. The highest used content (2 wt%) of excess-carbon yields TiC with the highest carbon content and minimal oxygen substitutes, which leads to the Ti3 AlC2 MAX phase with improved crystallinity and atomic stoichiometry, and finally Ti3 C2 Tx MXene with the highest electrical conductivity (11738 S cm-1 ) and superior electromagnetic shielding effectiveness. Additionally, the effects of carbon content and substitutional oxygen on the physical properties of TiC and Ti3 AlC2 are elucidated by density-functional-theory calculations. This inexpensive TiO2 -based method of synthesizing high-quality Ti3 C2 Tx MXene can facilitate large-scale production and thus accelerate global research on MXenes.

Biocompatible and Oxidation-Resistant Ti3 C2 Tx MXene with Halogen-Free Surface Terminations.

Surface chemistry influences not only physicochemical properties but also safety and applications of MXene nanomaterials. Fluorinated Ti3 C2 Tx MXene, synthesized using conventional HF-based etchants, raises concerns regarding harmful effects on electronics and toxicity to living organisms. In this study, well-delaminated halogen-free Ti3 C2 Tx flakes are synthesized using NaOH-based etching solution. The transversal surface plasmon mode of halogen-free Ti3 C2 Tx MXene (833 nm) confirmed red-shift compared to conventional Ti3 C2 Tx (752 nm), and the halogen-free Ti3 C2 Tx MXene has a different density of state by the high proportion of -O and -OH terminations. The synthesized halogen-free Ti3 C2 Tx exhibits a lower water contact angle (34.5°) and work function (3.6 eV) than those of fluorinated Ti3 C2 Tx (49.8° and 4.14 eV, respectively). The synthesized halogen-free Ti3 C2 Tx exhibits high biocompatibility with the living cells, as evidenced by no noticeable cytotoxicity, even at very high concentrations (2000 µg mL⁻1 ), at which fluorinated Ti3 C2 Tx caused ≈50% reduction in cell viability upon its oxidation. Additionally, the oxidation stability of halogen-free Ti3 C2 Tx is enhanced unexpectedly, which cumulatively provides a good rationale for pursuing the halogen-free routes for synthesizing MXene materials for their uses in biomedical and therapeutic applications.

Universal Ligands for Dispersion of Two-Dimensional MXene in Organic Solvents.

Ligands can control the surface chemistry, physicochemical properties, processing, and applications of nanomaterials. MXenes are the fastest growing family of two-dimensional (2D) nanomaterials, showing promise for energy, electronic, and environmental applications. However, complex oxidation states, surface terminal groups, and interaction with the environment have hindered the development of organic ligands suitable for MXenes. Here, we demonstrate a simple, fast, scalable, and universally applicable ligand chemistry for MXenes using alkylated 3,4-dihydroxy-l-phenylalanine (ADOPA). Due to the strong hydrogen-bonding and π-electron interactions between the catechol head and surface terminal groups of MXenes and the presence of a hydrophobic fluorinated alkyl tail compatible with organic solvents, the ADOPA ligands functionalize MXene surfaces under mild reaction conditions without sacrificing their properties. Stable colloidal solutions and highly concentrated liquid crystals of various MXenes, including Ti2CTx, Nb2CTx, V2CTx, Mo2CTx, Ti3C2Tx, Ti3CNTx, Mo2TiC2Tx, Mo2Ti2C3Tx, and Ti4N3Tx, have been produced in various organic solvents. Such products offer excellent electrical conductivity, improved oxidation stability, and excellent processability, enabling applications in flexible electrodes and electromagnetic interference shielding.

Controllable Surface-Grafted MXene Inks for Electromagnetic Wave Modulation and Infrared Anti-Counterfeiting Applications.

Two-dimensional transition metal carbide/nitride (MXene) conductive inks are promising for scalable production of printable electronics, electromagnetic devices, and multifunctional coatings. However, the susceptible oxidation and poor rheological property seriously impede the printability of MXene inks and the exploration of functional devices. Here, we proposed a controllable surface grafting strategy for MXene flakes (p-MXene) with prepolymerized polydopamine macromolecules to protect against water and oxygen, enrich surface chemistry, and significantly optimize the rheological properties of the inks. The obtained p-MXene inks can adapt to screen-printing and other high-viscosity processing techniques, facilitating the development of patterned electromagnetic films and coatings. Interestingly, the printed MXene polarizer can freely switch and quantitatively control microwave transmission, giving an inspiring means for smart microwave modulation beyond the commonly reported shielding function. Moreover, the introduction of polydopamine nanoshell enables the infrared emissivity of MXene coating to be adjusted to a large extent, which can produce infrared anti-counterfeiting patterns in a thermal imager. Therefore, multifunctional antioxidant p-MXene inks will greatly extend the potential applications for the next-generation printable electronics and devices.

Texture Regulation of Metal-Organic Frameworks, Microwave Absorption Mechanism-Oriented Structural Optimization and Design Perspectives.

Texture regulation of metal-organic frameworks (MOFs) is essential for controlling their electromagnetic wave (EMW) absorption properties. This review systematically summarizes the recent advancements in texture regulation strategies for MOFs, including etching and exchange of central ions, etching and exchange of ligands, chemically induced self-assembly, and MOF-on-MOF heterostructure design. Additionally, the EMW absorption mechanisms in approaches based on structure-function dependencies, including nano-micro topological engineering, defect engineering, interface engineering, and hybrid engineering, are comprehensively explored. Finally, current challenges and future research orientation are proposed. This review aims to provide new perspectives for designing MOF-derived EMW-absorption materials to achieve essential breakthroughs in mechanistic investigations in this promising field.

Tunable Ti3C2Tx MXene-Derived TiO2 Nanocrystals at Controlled pH and Temperature.

While two-dimensional (2D) Ti3C2Tx MXene in aqueous dispersions spontaneously oxidizes into titanium dioxide (TiO2) nanocrystals, the crystallization mechanism has not been comprehensively understood and the resultant crystal structures are not controlled among three representative polymorphs: anatase, rutile, and brookite. In this study, such control on the lattice structures and domain sizes of the MXene-derived TiO2 crystallites is demonstrated by means of the oxidation conditions, pH, and temperature (3.0-11.0 and 20-100 °C, respectively). It is observed that the formation of anatase phase is preferred against rutile phase in more basic and hotter oxidizing solutions, and even 100% anatase can be obtained at pH 11.0 and 100 °C. At lower pH and temperature, the portion of rutile phase increases such that it reaches ∼70% at pH 3 and 20 °C. Under certain circumstances, small portion of brookite phase is also observed. Smaller domain sizes of both anatase and rutile phases are observed in more basic oxidizing solutions and at lower temperatures. Based on these experimental results, we propose the crystallization mechanism in which the oxidative dissociation of Ti3C2Tx first produces Ti ions as the intermediate state, and they bind to abundant oxygen in the aqueous dispersions, and nucleate and crystallize into TiO2.

Field-induced orientational switching produces vertically aligned Ti3C2Tx MXene nanosheets.

Controlling the orientation of two-dimensional materials is essential to optimize or tune their functional properties. In particular, aligning MXene, a two-dimensional carbide and/or nitride material, has recently received much attention due to its high conductivity and high-density surface functional group properties that can easily vary based on its arranged directions. However, erecting 2D materials vertically can be challenging, given their thinness of few nanometres. Here, vertical alignment of Ti3C2Tx MXene sheets is achieved by applying an in-plane electric field, which is directly observed using polarised optical microscopy and scanning electron microscopy. The electric field-induced vertical alignment parallel to the applied alternating-current field is demonstrated to be reversible in the absence of a field, back to a random orientation distribution. Interdigitated electrodes with uniaxially aligned MXene nanosheets are demonstrated. These can be further modulated to achieve various patterns using diversified electrode substrates. Anisotropic electrical conductivity is also observed in the uniaxially aligned MXene nanosheet film, which is quite different from the randomly oriented ones. The proposed orientation-controlling technique demonstrates potential for many applications including sensors, membranes, polarisers, and general energy applications.

Fast and High-Yield Anhydrous Synthesis of Ti3 C2 Tx MXene with High Electrical Conductivity and Exceptional Mechanical Strength.

2D transition metal carbides or nitrides (MXenes) have attracted considerable attention from materials scientists and engineers owing to their physicochemical properties. Currently, MXenes are synthesized from MAX-phase precursors using aqueous HF. Here, in order to enhance the production of MXenes, an anhydrous etching solution is proposed, consisting of dimethylsulfoxide as solvent with its high boiling point, NH4 HF2 as an etchant, CH3 SO3 H as an acid, and NH4 PF6 as an intercalant. The reaction temperature can be increased up to 100 °C to accelerate the etching and delamination of Ti3 AlC2 MAX crystals; in addition, the destructive side reaction of the produced Ti3 C2 Tx MXene is suppressed in the etchant. Consequently, the etching reaction is completed in 4 h at 100 °C and produces high-quality monolayer Ti3 C2 Tx with an electrical conductivity of 8200 S cm-1 and yield of over 70%. The Ti3 C2 Tx MXene fabricated via this modified synthesis exhibits different surface structures and properties arising from more F-terminations than those of Ti3 C2 Tx synthesized in aqueous HF2 T. The atypical surface structure of Ti3 C2 Tx MXene results in an exceptionally high ultimate tensile strength (167 ± 8 MPa), which is five times larger than those of Ti3 C2 Tx MXenes synthesized in aqueous HF solution (31.7 ± 7.8 MPa).

Flexible and Transparent Electrode of Hybrid Ti3C2TX MXene-Silver Nanowires for High-Performance Quantum Dot Light-Emitting Diodes.

The development of electrodes with high conductivity, optical transparency, and reliable mechanical flexibility and stability is important for numerous solution-processed photoelectronic applications. Although transparent Ti3C2TX MXene electrodes with high conductivity are promising, their suitability for displays remains limited because of the high sheet resistance, which is caused by undesirable flake junctions and surface roughness. Herein, a flexible and transparent electrode has been fabricated that is suitable for a full-solution-processed quantum dot light-emitting diode (QLED). An MXene-silver nanowire (AgNW) hybrid electrode (MXAg) consists of a highly conductive AgNW network mixed with solution-processed MXene flakes. Efficient welding of wire-to-wire junctions with MXene flakes yields an electrode with a low sheet resistance and a high transparency of approximately 13.9 Ω sq-1 and 83.8%, respectively. By employing a thin polymer buffer layer of poly(methyl methacrylate) (PMMA), followed by mild thermal treatment, a hybrid PMMA-based MXene-AgNW (MXAg@PMMA) electrode in which the work function of an MXAg hybrid FTE physically embedded in PMMA (MXAg@PMMA) can be tuned by controlling the amount of MXene in the hybrid film facilitates the development of a high-performance solution-processed QLED that exhibits maximum external quantum and current efficiencies of approximately 9.88% and 25.8 cd/A, respectively, with excellent bending stability. This work function-tunable flexible transparent electrode based on solution-processed nanoconductors provides a way to develop emerging high-performance, wearable, cost-effective, and soft electroluminescent devices.

Multidimensional Ti3C2Tx MXene Architectures via Interfacial Electrochemical Self-Assembly.

An effective pathway to build macroscopic scale functional architectures bearing diverse structural dimensions is one of the critical challenges in the two-dimensional (2D) MXene research area. Unfortunately, assembling MXene without adhesive binder is largely limited due to its innate brittle nature and the relatively weak inter-flake van der Waals contact, in contrast to other mechanically compliant 2D materials such as graphene. Herein, an electrochemical self-assembly of pure Ti3C2Tx MXenes is presented for functional multidimensional MXene structures, effectively driven by layer-by-layer spontaneous interfacial reduction at metal template surfaces and subsequent defunctionalization. A three-dimensional open porous aerogel as well as 2D highly stacked thin film structures could be readily obtained in this approach, along with largely enhanced electrical properties induced by spontaneous removal of charge-trapping oxygen functional groups. Accordingly, supercapacitors and electromagnetic interference shielding films based on the multidimensional assembly demonstrate excellent performances.

Polymer-Laminated Ti3C2TX MXene Electrodes for Transparent and Flexible Field-Driven Electronics.

MXenes (Ti3C2TX) are two-dimensional transition-metal carbides and carbonitrides with high conductivity and optical transparency. However, transparent MXene electrodes with high environmental stability suitable for various flexible organic electronic devices have rarely been demonstrated. By laminating a thin polymer film onto a solution-processed MXene layer to protect the MXene film from harsh environmental conditions, we present transparent and flexible MXene electronic devices. A thin polymer layer spin-coated onto a transparent MXene electrode provides environmental stability even under air exposure longer than 7 d at high temperatures (up to 70 °C) and humidity levels (up to 50%) without degrading the transparency of the electrode. The resulting polymer-laminated (PL) MXene electrode facilitates the development of a variety of field-driven photoelectronic devices by exploiting the electric field exerted between the MXene layer and the counter electrode through the insulating polymer. Field-induced electroluminescent displays, based on both organic and inorganic phosphors, with PL-MXene electrodes are demonstrated with high transparency and mechanical flexibility. Furthermore, our PL-MXene electrode exhibits high versatility through successful implementation in capacitive-type pressure sensors and triboelectric nanogenerators, resulting in field-driven sensing and energy harvesting electronic devices with excellent operation reliability.

Mechanism and Kinetics of Oxidation Reaction of Aqueous Ti3C2Tx Suspensions at Different pHs and Temperatures.

Understanding the oxidation reaction of aqueous Ti3C2Tx MXene suspensions is very important for fostering fundamental academic studies as well as widespread industrial applications. Herein, we investigated the mechanism and kinetics of the oxidation reaction of aqueous Ti3C2Tx suspensions at various pH and temperature conditions. Through comprehensive analysis, the mechanism of the chemical oxidative degradation of aqueous Ti3C2Tx colloids was established. Chemical oxidation produces solid products such as TiO2 and amorphous carbon as well as various gaseous species including CH4, CO, CO2, and HF. Additionally, our comprehensive kinetic study proposes that aqueous Ti3C2Tx dispersions are degraded via an acid-catalyzed oxidation reaction, where, under acidic conditions, the protonation of the hydroxyl terminal groups on the Ti3C2Tx flakes induces electron localization on titanium atoms and accelerates their oxidation reaction. In contrast, under basic conditions, the electrostatically alkali-metalized hydroxyl intermediates forming a bulky solvent cage results in less electron localization on titanium atoms, and thus retards their oxidative degradation.

Improving oxidation stability of 2D MXenes: synthesis, storage media, and conditions.

Understanding and preventing oxidative degradation of MXene suspensions is essential for fostering fundamental academic studies and facilitating widespread industrial applications. Owing to their outstanding electrical, electrochemical, optoelectronic, and mechanical properties, MXenes, an emerging class of two-dimensional (2D) nanomaterials, show promising state-of-the-art performances in various applications including electromagnetic interference (EMI) shielding, terahertz shielding, electrochemical energy storage, triboelectric nanogenerators, thermal heaters, light-emitting diodes (LEDs), optoelectronics, and sensors. However, MXene synthesis using harsh chemical etching causes many defects or vacancies on the surface of the synthesized MXene flakes. Defective sites are vulnerable to oxidative degradation reactions with water and/or oxygen, which deteriorate the intrinsic properties of MXenes. In this review, we demonstrate the nature of oxidative degradation of MXenes and highlight the recent advancements in controlling the oxidation kinetics of MXenes with several promising strategic approaches, including careful control of the quality of the parent MAX phase, chemical etching conditions, defect passivation, dispersion medium, storage conditions, and polymer composites.

Reduction of Electrochemically Exfoliated Graphene Films for High-Performance Electromagnetic Interference Shielding.

Two-dimensional graphene is of great interest for electromagnetic interference (EMI) shielding owing to its inherent electrical conductivity, lightweight, and excellent mechanical flexibility even at minor thicknesses. However, the complex synthesis and quality-control difficulties limit its application. In this study, we demonstrate that electrochemically exfoliated graphene (EEG) with post-reduction treatment is a promising candidate for lightweight EMI shielding materials. A facile electrochemical exfoliation approach produces a high-quality multilayer graphene with a high electrical conductivity of ∼600 S cm-1, owing to its low degree of oxidation. The reduction of EEG by three different methods, including chemical, thermal, and microwave treatments, causes the removal of surface functional groups as well as significant changes in the microstructure of the final films. The reduced graphene films by microwaves, which are driven by the improved electrical conductivity and large volume expansion, exhibit an EMI shielding effectiveness of 108 dB at a thickness of 125 µm, one of the largest EMI shielding values ever reported for graphene at comparable thicknesses.

2D Transition Metal Carbides (MXenes): Applications as an Electrically Conducting Material.

Since their discovery in 2011, 2D transition metal carbides, nitrides, and carbonitrides, known as MXenes, have attracted considerable global research interest owing to their outstanding electrical conductivity coupled with light weight, flexibility, transparency, surface chemistry tunability, and easy solution processability. Here, the promising abilities of 2D MXenes, from both experimental and theoretical perspectives, for designing conductive materials for a range of applications, including electromagnetic interference shielding, flexible optoelectronics, sensors, and thermal heaters, are presented.