Solution-processed nanomaterials can be assembled by a range of interfacial techniques, including as stabilizers in Pickering emulsions. Two-dimensional (2D) materials present a promising route toward nanosheet-stabilized emulsions for functional segregated networks, while also facilitating surface energy studies. Here, we demonstrate emulsions stabilized by the 2D materials including the transition metal carbide MXene, titanium carbide (Ti3C2T x ), and develop an approach for in situ measurement of nanosheet surface energy based on emulsion inversion. This approach is applied to determine the influence of pH and nanosheet size on surface energy for MXene, graphene oxide, pristine graphene, and molybdenum disulfide. The surface energy values of hydrophilic Ti3C2T x and graphene oxide decrease significantly upon protonation of usually dissociated functional groups, facilitating emulsion stabilization. Similarly, pristine graphene and molybdenum disulfide increase in surface energy when their surface functional groups are deprotonated under basic conditions. In addition, the surface energies of these pristine materials are correlated with nanosheet size, which allows for the calculation of the basal plane and edge surface energies of pristine nanosheets. This understanding of surface energies and control of emulsion inversion will allow design of emulsion-templated structures and surface energy studies of a wide range of solution-processable nanomaterials.

MXenes, a relatively new class of two-dimensional (2D) transition-metal carbides, carbonitrides, and nitrides, exhibit unique properties such as high electronic conductivity, a wide range of optical characteristics, hydrophilicity, and mechanical stability. Because of the high electronic conductivity, MXenes have shown promise in many applications, such as energy storage, electromagnetic interference shielding, antennas, and transparent coatings. 2D titanium carbide (Ti3C2Tx, where T-x represents surface terminations), the first discovered and most studied MXene, has the highest electronic conductivity exceeding 10 000 S cm(-1). There have been several efforts to alter the conductivity of MXenes, such as manipulation of the transition-metal layer and control of surface terminations. However, the impact of the C and N site composition on electronic transport has not been explored. In this study, the effects of synthesis methods on optoelectronic properties of 2D titanium carbonitride, Ti3CNTx, were systematically investigated. We show that Ti3CNTx, which hosts a mix of carbon and nitrogen atoms in the X layer, has lower electronic conductivity and a blue shift of the main absorption feature within the UV-visible spectrum, compared to Ti3C2Tx. Moreover, intercalants such as water and tetraalkylammonium hydroxides decrease the electronic conductivity of MXene due to increased interflake resistance, leading to an increase in resistivity with decreasing temperature as observed in ensemble transport measurements. When the intercalants are removed, Ti3CNTx exhibits its intrinsic metallic behavior in good agreement with Hall measurements and transport properties measured on single-flake field-effect transistor devices. The dependence of conductivity of Ti3CNTx on the presence of intercalants opens wide opportunities for creating MXene-based materials with tunable electronic properties.

MXenes are an emergent class of two-dimensional materials with a very wide spectrum of promising applications. The synthesis of multiple MXenes, specifically solid-solution MXenes, allows fine tuning of their properties, expands their range of applications, and leads to enhanced performance. The functionality of solid-solution MXenes is closely related to the valence state of their constituents: transition metals, oxygen, carbon, and nitrogen. However, the impact of changes in the oxidation state of elements in MXenes is not well understood. In this work, three interrelated solid-solution MXene systems (Ti2−y Nb y CT x , Nb2−y V y CT x , and Ti2−y V y CT x ) were investigated with scanning transmission electron microscopy and electron energy-loss spectroscopy to determine the localized valence states of metals at the nanoscale. The analysis demonstrates changes in the electronic configuration of V upon modification of the overall composition and within individual MXene flakes. These shifts of oxidation state can explain the nonlinear optical and electronic features of solid-solution MXenes. Vanadium appears to be particularly sensitive to modification of the valence state, while titanium maintains the same oxidation state in Ti–Nb and Ti–V MXenes, regardless of stoichiometry. The study also explains Nb’s influential role in the previously observed electronic properties in the Nb–V and Nb–Ti systems.

Delamination of two-dimensional materials is a requisite step for exploiting their unique properties. Herein, we report on the formation of stable colloidal solutions of Ti3C2 and Mo2Ti2C3 MXene nanosheets by the dispersion and electrostatic exfoliation of stacked multilayer MXenes in the presence of albumin. Delamination of multilayered MXenes into atomically thin nanosheets resulted in stable colloidal solutions with good stability due to the adsorption of albumin, which prevents re-aggregation of the few-layer nanosheets. Cascading centrifugation was used to produce monodisperse colloids. This study demonstrates a processing method that can be utilized to prepare MXenes for biomedical applications. Since protein adsorption onto nanomaterial surfaces plays a significant role in many fields, including medicine, biology, pharmaceuticals, and environmental engineering, albumin coated MXenes may find many applications.

Transition metal carbides and nitrides (MXenes) are a relatively new class of 2D materials, which include metallic and semiconducting examples. The chemical compositions of the vast MXene family span a broad range of the periodic table, yet the optical spectra of only a handful of MXene compositions have been reported, and in only one example are the spectroscopic features assigned. The optical properties of nine carbide MXenes, representing a systematic variation of chemical composition and atomic structure are presented here. The observed optical phenomena span the UV to IR and include interband transitions and plasma excitations. The spectral features involving excitation of the plasma provide an optical readout of the composition-dependent carrier concentration, revealing even subtle changes due to modification of the surface chemistry. The high carrier concentration found in many MXenes differentiates them from other known 2D materials and the authors present evidence in favor of the hypothesis that MXenes host optically active plasmon resonances that naturally span the UV to near-IR, as a function of composition. This study introduces optical properties of novel MXenes, benefits the interpretation of 2D materials spectroscopy, and suggests the tremendous potential for this class of optoelectronic building blocks.

MXenes, a large family of two-dimensional materials, have attracted tremendous attention due to their unique physical and chemical properties. Reversible ion intercalation between MXene layers allows modification of the optical, thermal, magnetic, and chemical properties. The electrochemical charge/discharge of MXenes in aqueous electrolytes was reported to lead to reversible electrochromic behavior. In this work, the electrochromic effect of semitransparent Ti3C2Tx MXene film was probed by electrochemical intercalation of Li ions. Correspondingly, a peak shift of 100 nm was observed in the UV-vis spectrum. By combining in-situ Raman spectroscopy, in-situ X-ray diffraction, and density functional theory calculations, we show that the electrochromic shift is primarily due to the formation of robust O-Li bonds and the emerging bands induced changes of inter-band excitations. Understanding the mechanism of electrochromic behavior in Ti3C2Tx lays the foundations of designating 2D materials with durable, controllable, and efficient intercalation-induced electrochromic behaviors.

One of the primary factors limiting further research and the commercial use of the two-dimensional (2D) MXene titanium carbide (Ti3C2), as well as MXenes in general, is the rate at which freshly made samples oxidize and degrade when stored as aqueous suspensions. Here, we show that including excess aluminum during synthesis of the Ti3AlC2 MAX phase precursor leads to the creation of Ti3AlC2 grains with improved stoichiometry and crystallinity. Ti3C2 nanosheets produced from the improved Ti3AlC2 are of higher quality, as evidenced by their increased resistance to oxidation and an increase in their electrical conductivity to 20,000 S/cm. Our results indicate that defects created during the synthesis of Ti3C2 (and by inference, other MXenes) lead to the previously observed instability. We show that by eliminating those defects results in Ti3C2 that is highly stable in aqueous solutions and in air. Aqueous suspensions of single- to few-layer Ti3C2 flakes produced from the modified Ti3AlC2 have a shelf life of over ten months, compared to one to two weeks for Ti3C2 produced from conventional Ti3AlC2, even when stored in ambient conditions. Freestanding films made from Ti3C2 suspensions stored for ten months show minimal decreases in electrical conductivity and negligible oxidation. Oxidation of the improved Ti3C2 in air initiates at temperatures that are 100-150°C higher than conventional Ti3C2. The observed improvements in both the shelf life and properties of Ti3C2 will facilitate the widespread use of this material.

MXenes have shown record-breaking redox capacitance in aqueous electrolytes, but in a limited voltage window due to oxidation under anodic potential and hydrogen evolution under high cathodic potential. Coupling Ti3C2Tx MXene negative electrode with RuO2 or carbon-based positive electrodes expanded the voltage window in sulfuric acid electrolyte to about 1.5 V. Here, we present an asymmetric pseudocapacitor using abundant and eco-friendly vanadium doped MnO2 as the positive and Ti3C2Tx MXene as the negative electrode in a neutral 1 M Li2SO4 electrolyte. This all-pseudocapacitive asymmetric device not only uses a safer electrolyte and is a much less expensive counter-electrode than RuO2, but also can operate within a 2.1 V voltage window, leading to a maximum energy density of 46 Wh/kg. This study also demonstrates the possibility of using MXene electrodes to expand the working voltage window of traditional redox-capable materials.

Metal-semiconductor heterostructures are believed to improve hot-electron injection efficiency and influence the photocatalytic performance. Understanding the carrier dynamics at the heterostructure is essential for designing more efficient photocatalysts. Herein, we fabricated a Schottky heterostructure using two-dimensional (2D) titanium carbide MXene (Ti3C2Tx, where T-x stands for surface terminations, such as O or OH) and a TiO2 semiconductor and examined the carrier dynamics at the heterostructure using time-resolved infrared techniques. MXene exhibits robust metallic properties in terms of photoconductivity comparable to those of high-quality 2D graphene materials. The photoexcitation of MXene greatly increases the scattering rate and leads to a decreased photoconductivity. When Ti3C2Tx comes in close contact with the TiO2 semiconductor, band bending leads to the formation of a Schottky barrier at the contact junction. In this plasmonic TiO2/Ti3C2Tx heterostructure, hot electrons are excited only from MXene upon photon absorption at wavelengths far below the TiO2 band gap. Under these conditions, the Ti3C2Tx-generated plasmonic electrons are transferred into the conduction band of the TiO2 semiconductor over the Schottky barrier with a fast time constant of 180 fs. The strong electronic coupling between oxygen-terminated Ti3C2Tx and TiO2 is due to their proximity, and the resulting interactions are likely responsible for the fast electron transfer in the composites. Our results demonstrate a potential of 2D MXene materials in plasmonic applications and provide new insights into the design of MXene-based photocatalysts.

Alloying is a long-established strategy to tailor properties of metals for specific applications, thus retaining or enhancing the principal elemental characteristics while offering additional functionality from the added elements. We propose a similar approach to the control of properties of two-dimensional transition metal carbides known as MXenes. MXenes (Mn+1Xn) have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites presents promising routes for tailoring the chemical, optical, electronic, or mechanical properties of MXenes. Herein, we systematically investigated three interrelated binary solid-solution MXene systems based on Ti, Nb, and/or V at the M-site in a M2XTx structure (Ti2-yNbyCTx, Ti2-yVyCTx, and V2-yNbyCTx, where Tx stands for surface terminations) showing the evolution of electronic and optical properties as a function of composition. All three MXene systems show unlimited solubility and random distribution of metal elements in the metal sublattice. Optically, the MXene systems are tailorable in a nonlinear fashion, with absorption peaks from ultraviolet to near-infrared wavelength. The macroscopic electrical conductivity of solid solution MXenes can be controllably varied over 3 orders of magnitude at room temperature and 6 orders of magnitude from 10 to 300 K. This work greatly increases the number of nonstoichiometric MXenes reported to date and opens avenues for controlling physical properties of different MXenes with a limitless number of compositions possible through M-site solid solutions.

Wearable sensors for surface electromyography (EMG) are composed of single- to few-channel large-area contacts, which exhibit high interfacial impedance and require conductive gels or adhesives to record high-fidelity signals. These devices are also limited in their ability to record activation across large muscle groups due to poor spatial coverage. To address these challenges, we have developed a novel high-density EMG array based on titanium carbide (Ti3C2Tx) MXene encapsulated in parylene-C. Ti3C2Tx is a two-dimensional nanomaterial with excellent electrical, electrochemical, and mechanical properties, which forms colloidally stable aqueous dispersions, enabling safe, scalable solutions-processing. Leveraging the excellent combination of metallic conductivity, high pseudocapacitance, and ease of processability of Ti3C2Tx MXene, we demonstrate the fabrication of gel-free, high-density EMG arrays which are ~8 μm thick, feature 16 recording channels, and are highly skin-conformable. The impedance of Ti3C2Tx electrodes in contact with human skin is 100-1000x lower than the impedance of commercially-available electrodes which require conductive gels to be effective. Furthermore, our arrays can record high-fidelity, low-noise EMG, and can resolve muscle activation with improved spatiotemporal resolution and sensitivity compared to conventional gelled electrodes. Overall, our results establish Ti3C2Tx-based bioelectronic interfaces as a powerful platform technology for high-resolution, non-invasive wearable sensing technologies.

Two-dimensional transition metal carbides and nitrides (MXenes) have accumulated tremendous interest recently due to their high conductivity and excellent figures of merit in electromagnetic interference shielding and other applications. Large-area freestanding films of MXenes are important for versatility in application; however, alternative processing methods are needed for large-scale production. In this work, we demonstrate fabrication of Ti3C2Tx MXene freestanding films through drop-casting onto hydrophobic plastic substrates. Freestanding MXene films prepared using the drop-casting method can be fabricated in large areas (>125 cm(2)) and thicknesses (23.2 mm), and have smooth surfaces (14 nm RMS roughness) while maintaining high electrical conductivity (similar to 7,000 S cm(-1)). Moreover, these MXene films can be micropatterned in three dimensions by processing on commercially available microstructured plastics, resulting in a 38% increase in normalized electromagnetic interference shielding efficiency compared with flat films. The results presented here suggest a scalable path toward creating MXene freestanding films for prototypes and industrialization.

Control of lasing properties through tailorable and dynamically tunable materials and reconfigurable compositions can augment the performance of random lasers for a wide range of applications. Here, a colloid of randomly dispersed weakly scattering single-layer titanium carbide (Ti 3 C 2 T x ) MXene flakes embedded within rhodamine 101 gain medium is experimentally shown to provide feedback for random lasing. Additionally, in contrast to previously reported random laser systems where the optical properties of scatterers are static, the relative permittivity of Ti 3 C 2 T x MXene flakes can be varied under optical pumping due to the saturable absorption properties. Numerical simulations indicate that the observed nonlinear response of Ti 3 C 2 T x MXene flakes enables dynamically tunable random lasing. Thus, pumping the Ti 3 C 2 T x MXene flakes with a second optical source decreases the gain threshold required to obtain random lasing. Also, using numerical simulations, it is shown that the control over the intensity of the second pump enables tuning the field distribution of the random lasing modes. Considering the diversity of the MXenes family, the proposed MXene colloidal metamaterial design opens up a new avenue to advanced control of lasing properties for photonic applications.

Although several transparent conducting materials such as carbon nanotubes, graphene, and conducting polymers have been intensively explored as flexible electrodes in optoelectronic devices, their insufficient electrical conductivity, low work function, and complicated electrode fabrication processes have limited their practical use. Herein, a 2D titanium carbide (Ti3 C2 ) MXene film with transparent conducting electrode (TCE) properties, including high electrical conductivity (≈11 670 S cm-1 ) and high work function (≈5.1 eV), which are achieved by combining a simple solution processing with modulation of surface composition, is described. A chemical neutralization strategy of a conducting-polymer hole-injection layer is used to prevent detrimental surface oxidation and resulting degradation of the electrode film. Use of the MXene electrode in an organic light-emitting diode leads to a current efficiency of ≈102.0 cd A-1 and an external quantum efficiency of ≈28.5% ph/el, which agree well with the theoretical maximum values from optical simulations. The results demonstrate the strong potential of MXene as a solution-processable electrode in optoelectronic devices and provide a guideline for use of MXenes as TCEs in low-cost flexible optoelectronic devices.

The development of stretchable electronics requires the invention of compatible high-performance power sources, such as stretchable supercapacitors and batteries. In this work, two-dimensional (2D) titanium carbide (Ti3C2Tx) MXene is being explored for flexible and printed energy storage devices by fabrication of a robust, stretchable high-performance supercapacitor with reduced graphene oxide (RGO) to create a composite electrode. The Ti3C2Tx/RGO composite electrode combines the superior electrochemical and mechanical properties of Ti3C2Tx and the mechanical robustness of RGO resulting from strong nanosheet interactions, larger nanoflake size, and mechanical flexibility. It is found that the Ti3C2Tx/RGO composite electrodes with 50 wt % RGO incorporated prove to mitigate cracks generated under large strains. The composite electrodes exhibit a large capacitance of 49 mF/cm2 (∼490 F/cm3 and ∼140 F/g) and good electrochemical and mechanical stability when subjected to cyclic uniaxial (300%) or biaxial (200% × 200%) strains. The as-assembled symmetric supercapacitor demonstrates a specific capacitance of 18.6 mF/cm2 (∼90 F/cm3 and ∼29 F/g) and a stretchability of up to 300%. The developed approach offers an alternative strategy to fabricate stretchable MXene-based energy storage devices and can be extended to other members of the large MXene family.

Decreasing the size of portable, wearable, and integrated electronics requires subsequent reduction in the accompanying energy storage devices. To further decrease the size of supercapacitors without compromising device performance, adequate materials are required as well as appropriate device design. Traditionally, carbon nanomaterials have been utilized within high-performance electrochemical energy storage applications, however carbides, specifically two-dimensional (2D) transition metal carbides and or nitrides (MXenes) have shown promise. Herein, a focused-ion-beam (FIB) process is used for patterning of titanium carbide (Ti3C2) carbon nanotube (CNT) electrodes into a finely controlled coplanar interdigitated configuration. The symmetric micro supercapacitors produced have a narrow, 500 nm gap between the electrode fingers and exhibit high areal capacitance of similar to 317 mF cm(-2) at a scan rate of 50 mV s(-1) and still retain >30% of their capacitance (similar to 104 mF cm(-2)) at 100 V s(-1). In addition, electron beam lithography and photolithography are utilized to create almost invisible devices with ultra-small footprints (0.04 mm(2) device areas) that can be used for securing electronic components. This study provides a simple and reliable method for fabrication of on-chip symmetric MSCs with coplanar interdigitated electrodes.

Implantable microelectrode technologies have been widely used to elucidate neural dynamics at the microscale to gain a deeper understanding of the neural underpinnings of brain disease and injury. As electrodes are miniaturized to the scale of individual cells, a corresponding rise in the interface impedance limits the quality of recorded signals. Additionally, conventional electrode materials are stiff, resulting in a significant mechanical mismatch between the electrode and the surrounding brain tissue, which elicits an inflammatory response that eventually leads to a degradation of the device performance. To address these challenges, we have developed a process to fabricate flexible microelectrodes based on Ti3C2 MXene, a recently discovered nanomaterial that possesses remarkably high volumetric capacitance, electrical conductivity, surface functionality, and processability in aqueous dispersions. Flexible arrays of Ti3C2 MXene microelectrodes have remarkably low impedance due to the high conductivity and high specific surface area of the Ti3C2 MXene films, and they have proven to be exquisitely sensitive for recording neuronal activity. In this protocol, we describe a novel method for micropatterning Ti3C2 MXene into microelectrode arrays on flexible polymeric substrates and outline their use for in vivo micro-electrocorticography recording. This method can easily be extended to create MXene electrode arrays of arbitrary size or geometry for a range of other applications in bioelectronics and it can also be adapted for use with other conductive inks besides Ti3C2 MXene. This protocol enables simple and scalable fabrication of microelectrodes from solution-based conductive inks, and specifically allows harnessing the unique properties of hydrophilic Ti3C2 MXene to overcome many of the barriers that have long hindered the widespread adoption of carbon-based nanomaterials for high-fidelity neural microelectrodes.

Two-dimensional transition metal carbides, nitrides and carbonitrides, popular by the name MXenes, are a promising class of materials as they exhibit intriguing optical, optoelectronic and electrochemical properties. Taking advantage of their metallic conductivity and hydrophilicity, titanium carbide MXenes (Ti3C2Tx and others) are used to fabricate solution processable transparent conducting electrodes (TCEs) for the design of three-electrode electrochromic cells. However, the tunable electrochromic behavior of various titanium-based MXene compositions across the entire visible spectrum has not yet been demonstrated. Here, we investigate the intrinsic electrochromic properties of titanium-based MXenes, Ti3C2Tx, Ti3CNTx, Ti2CTx, and Ti1.6Nb0.4CTx, where individual MXenes serve as a transparent conducting, electrochromic, and plasmonic material layer. Plasmonic extinction bands for Ti3C2Tx, Ti2CTx and Ti1.6Nb0.4CTx are centered at 800, 550 and 480 nm, which are electrochemically tunable to 630, 470 and 410 nm, respectively, whereas Ti3CNTx shows a reversible change in transmittance in the wide visible range. Additionally, the switching rates of MXene electrodes with no additional transparent conductor electrodes are estimated and correlated with the respective electrical figure of merit values. This study demonstrates that MXene-based electrochromic cells are tunable in the entire visible spectrum and suggests the potential of the MXene family of materials in optoelectronic, plasmonic, and photonic applications, such as tunable visible optical filters and modulators, to name a few.

While intraocular lenses (IOL) are used to restore visual acuity in cataract patients, they are limited in their development as no clinically available lens can effectively mimic the accommodative function of the eye's natural lens. The optoelectronic properties of 2D transition metal carbides and/or nitrides (MXenes), including high electronic conductivity, optical transparency, flexibility, biocompatibility, and hydrophilicity, suggest potential use within an accommodating IOL. This study investigates the use of Ti 3 C 2 T x (MXene) as a transparent, conductive electrode to allow changes in optical power. Ti 3 C 2 T x is synthesized and spin‐coated on hydrophobic acrylate IOLs, achieving a sheet resistance ranging from 0.2–1.0 kΩ sq −1 with 50–80% transmittance in the visible region. Human lens epithelial and monocytic cells show no cytotoxic nor inflammatory response to the coated lenses. An adjustable focus test cell is fabricated using a liquid crystal (LC) layer sandwiched between Ti 3 C 2 T x coatings on a solid support. Molecular reorientation of the LC layer, through an applied electric field, results in changes in optical power as objects viewed through the test cell appeared in and out of focus. This study is the first step toward the use of Ti 3 C 2 T x within an accommodative IOL design through demonstration of reversible, controlled, adjustable focus.

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of Mn+1XnTx, in which two, three, or four atomic layers of a transition metal (M: Ti, Nb, V, Cr, Mo, Ta, etc.) are interleaved with layers of C and/or N (shown as X), and Tx represents surface termination groups such as -OH, ═O, and -F. Here, we report the scalable synthesis and characterization of a MXene with five atomic layers of transition metals (Mo4VC4Tx), by synthesizing its Mo4VAlC4 MAX phase precursor that contains no other MAX phase impurities. These phases display twinning at their central M layers which is not present in any other known MAX phases or MXenes. Transmission electron microscopy and X-ray diffraction were used to examine the structure of both phases. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and high-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy were used to study the composition of these materials. Density functional theory calculations indicate that other five transition metal-layer MAX phases (M'4M″AlC4) may be possible, where M' and M″ are two different transition metals. The predicted existence of additional Al-containing MAX phases suggests that more M5C4Tx MXenes can be synthesized. Additionally, we characterized the optical, electronic, and thermal properties of Mo4VC4Tx. This study demonstrates the existence of an additional subfamily of M5X4Tx MXenes as well as a twinned structure, allowing for a wider range of 2D structures and compositions for more control over properties, which could lead to many different applications.