Treatment of carbon electrodes with Ti3C2Tx MXene coating and thermal method for vanadium redox flow batteries: a comparative study.

One of the significant challenges of vanadium redox flow batteries is connected to the negative electrode where the main reaction of V(ii)/V(iii) and the side reaction of hydrogen evolution compete. To address this issue, we used titanium carbide (Ti3C2Tx) MXene coating via drop-casting to introduce oxygen functional groups and metals on the carbon electrode surface. Characterization through scanning electron microscopy and X-ray photoelectron spectroscopy confirmed the even distribution of Ti3C2Tx MXene on the electrodes and the presence of titanium and termination groups (-O, -Cl, and -F). The cyclic voltammetry analysis of MXene-coated electrodes showed more sharp electrochemical peaks for the V(ii)/V(iii) reaction than thermal-treated electrodes, even at relatively high scan rates. Notably, a relatively high reaction rate of 5.61 × 10-4 cm s-1 was achieved for the V(ii)/V(iii) reaction on MXene-coated electrodes, which shows the competitiveness of the method compared to thermal treatment (4.17 × 10-4 cm s-1). The flow battery tests, at a current density of 130 mA cm-2, using MXene-coated electrodes showed pretty stable discharge capacity for over 100 cycles. In addition, the voltage and energy efficiency were significantly higher than those of the system using untreated electrodes. Overall, this work highlights the potential application of MXene coating in carbon electrode treatment for vanadium redox flow batteries due to remarkable electrocatalytic activity and battery performance, providing a competitive method for thermal treatment.

Accelerating 2D materials discovery.

A large-scale theory-driven approach predicts many new 2D materials.

The Evolution of MXenes Conductivity and Optical Properties Upon Heating in Air.

MXenes, a family of 2D transition-metal carbides and nitrides, have excellent electrical conductivity and unique optical properties. However, MXenes oxidize in ambient conditions, which is accelerated upon heating. Intercalation of water also causes hydrolysis accelerating oxidation. Developing new tools to readily characterize MXenes' thermal stability can enable deeper insights into their structure-property relationships. Here, in situ spectroscopic ellipsometry (SE) is employed to characterize the optical properties of three types of MXenes (Ti3 C2 Tx , Mo2 TiC2 Tx , and Ti2 CTx ) with varied composition and atomistic structures to investigate their thermal degradation upon heating under ambient environment. It is demonstrated that changes in MXene extinction and optical conductivity in the visible and near-IR regions correlate well with the amount of intercalated water and hydroxyl termination groups and the degree of oxidation, measured using thermogravimetric analysis. Among the three MXenes, Ti3 C2 Tx and Ti2 CTx , respectively, have the highest and lowest thermal stability, indicating the role of transition-metal type, synthesis route, and the number of atomic layers in MXene flakes. These findings demonstrate the utility of SE as a powerful in situ technique for rapid structure-property relationship studies paving the way for the further design, fabrication, and property optimization of novel MXene materials.

High-throughput printing of combinatorial materials from aerosols.

The development of new materials and their compositional and microstructural optimization are essential in regard to next-generation technologies such as clean energy and environmental sustainability. However, materials discovery and optimization have been a frustratingly slow process. The Edisonian trial-and-error process is time consuming and resource inefficient, particularly when contrasted with vast materials design spaces1. Whereas traditional combinatorial deposition methods can generate material libraries2,3, these suffer from limited material options and inability to leverage major breakthroughs in nanomaterial synthesis. Here we report a high-throughput combinatorial printing method capable of fabricating materials with compositional gradients at microscale spatial resolution. In situ mixing and printing in the aerosol phase allows instantaneous tuning of the mixing ratio of a broad range of materials on the fly, which is an important feature unobtainable in conventional multimaterials printing using feedstocks in liquid-liquid or solid-solid phases4-6. We demonstrate a variety of high-throughput printing strategies and applications in combinatorial doping, functional grading and chemical reaction, enabling materials exploration of doped chalcogenides and compositionally graded materials with gradient properties. The ability to combine the top-down design freedom of additive manufacturing with bottom-up control over local material compositions promises the development of compositionally complex materials inaccessible via conventional manufacturing approaches.

Step-by-Step Guide for Synthesis and Delamination of Ti3 C2 Tx MXene.

To advance the MXene field, it is crucial to optimize each step of the synthesis process and create a detailed, systematic guide for synthesizing high-quality MXene that can be consistently reproduced. In this study, a detailed guide is provided for an optimized synthesis of titanium carbide (Ti3 C2 Tx ) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric-Ti3 AlC2 MAX phase and delamination of the etched multilayered Ti3 C2 Tx MXene using lithium chloride at 65 °C for 1 h with argon bubbling. The effect of different synthesis variables is investigated, including the stoichiometry of the mixed powders to synthesize Ti3 AlC2 , pre-etch impurity removal conditions, selective etching, storage, and drying of MXene multilayer powder, and the subsequent delamination conditions. The synthesis yield and the MXene film electrical conductivity are used as the two parameters to evaluate the MXene quality. Also the MXenes are characterized with scanning electron microscopy, x-ray diffraction, atomic force microscopy, and ellipsometry. The Ti3 C2 Tx film made via the optimized method shows electrical conductivity as high as ≈21,000 S/cm with a synthesis yield of up to 38 %. A detailed protocol is also provided for the Ti3 C2 Tx MXene synthesis as the supporting information for this study.

Effect of vacancies and edges in promoting water chemisorption on titanium-based MXenes.

The functionality of two-dimensional (2D) transition metal carbides and nitrides (MXenes) in technological applications greatly depends on their wettability. For instance, MXenes' layer stability against degradative oxidation is notably reduced when stored in aqueous solutions, leading to the transformation into oxides. In this work, we study water adsorption on Ti-based MXenes by ab initio calculations. The energy gains for the molecular adsorption on Tin+1XnT2 is evaluated as a function of the termination (T = F, O, OH, mixture), the carbon/nitrogen ratio (X = C, N), the layer thickness (n) and water coverage. MXenes' hydrophilicity tends to increase due to the presence of defects as vacancies and flake edges. We demonstrate that physical adsorption occurs through hydrogen bonding on both defect-free layers and layers containing C/N or Ti atomic vacancies, with -OH terminations providing the strongest interactions (0.40-0.65 eV). In contrast, strong water chemisorption is observed on surfaces with a single termination vacancy (0.60-1.20 eV), edges (0.75-0.85 eV), and clusters of defects (1.00-1.80 eV). We verified that the presence of undercoordinated Ti atoms on the surface is the key factor in promoting H2O chemisorption, i.e., the degradative oxidation.

Life-Cycle Assessment of Ti3 C2 Tx MXene Synthesis.

MXenes, 2D transition metal carbides, nitrides, and carbonitrides, have been investigated for diverse applications since their discovery; however, their life-cycle assessment (LCA) has not been studied. Here, a "cradle to gate" LCA is performed to assess the cumulative energy demand (CED) and environmental impacts of lab-scale synthesis of Ti3 C2 Tx , the most researched MXene composition. Electromagnetic interface (EMI) shielding is selected as it is one of MXenes' most promising applications and LCA of Ti3 C2 Tx synthesis is compared to aluminum and copper foils, two typical EMI-shielding materials. Two laboratory-scale MXene synthesis systems-gram and kilogram batches-are examined. The CED and environmental implications of Ti3 C2 Tx synthesis are investigated based on its precursor production, selective etching, delamination processes, laboratory location, energy mix, and raw material type. These results show that laboratory electricity usage for the synthesis processes accounts for >70% of the environmental impacts. Manufacturing 1.0 kg of industrial-scale aluminum and copper foil releases 23.0 kg and 8.75 kg of CO2 , respectively, while 1.0 kg of lab-scale MXene synthesis releases 428.10 kg. Chemical usage is less impactful than electricity, which suggests that recycled resources and renewable energy can make MXene synthesis more sustainable. Understanding MXene LCA helps the industrialization of this material.

MXene Free Standing Films: Unlocking the Impact of Flake Sizes in Microwave Resonant Structures in Humid Environments.

Microwave communication devices necessitate elements with high electrical conductivity, a property which was traditionally found in metals (e.g., copper). However, in applications such as satellite communications, metals prevent the payload from achieving lightweight and flexible characteristics. Here, we demonstrate the development of MXene film microwave resonators, leveraging MXene's high electrical conductivity and unique mechanical properties. To investigate resonant performance in humid conditions and study the effects of MXene's processing and treatment, MXene films with different flake sizes are prepared and exposed to cyclic humidity. For the large- and small-flake Ti3 C2 MXene films in cyclic humidity, the large-flake film demonstrates higher electrical conductivity, higher resonance quality factor (150 and 35 as unloaded, and loaded), and less fluctuation of performance (≈1.7% total shift in resonance frequency). Further, by implementing MXene films of two different diameters, the correlation between film size and resonant frequency is demonstrated. By introducing an active resonant configuration, the effect of MXene degradation and microwave losses can be compensated. This active feedback loop demonstrates a ≈300 times increase in the quality factor of MXene resonators. As a building block for terrestrial and satellite communication modules, MXene resonators potentiate the replacement of metals in achieving unique electrical and mechanical properties.

Double-Transition-Metal MXene Films Promoting Deeply Rechargeable Magnesium Metal Batteries.

Magnesium metal batteries are promising candidates for next-generation high-energy-density and low-cost energy storage systems. Their application, however, is precluded by infinite relative volume changes and inevitable side reactions of Mg metal anodes. These issues become more pronounced at large areal capacities that are required for practical batteries. Herein, for the first time, double-transition-metal MXene films are developed to promote deeply rechargeable magnesium metal batteries using Mo2 Ti2 C3 as a representative example. The freestanding Mo2 Ti2 C3 films, which are prepared using a simple vacuum filtration method, possess good electronic conductivity, unique surface chemistry, and high mechanical modulus. These superior electro-chemo-mechanical merits of Mo2 Ti2 C3 films help to accelerate electrons/ions transfer, suppress electrolyte decomposition and dead Mg formation, as well as maintain electrode structural integrity during long-term and large-capacity operation. As a result, the as-developed Mo2 Ti2 C3 films exhibit reversible Mg plating/stripping with high Coulombic efficiency of 99.3% at a record-high capacity of 15 mAh cm-2 . This work not only sheds innovative insights into current collector design for deeply cyclable Mg metal anodes, but also paves the way for the application of double-transition-metal MXene materials in other alkali and alkaline earth metal batteries.

MXenes Antibacterial Properties and Applications: A Review and Perspective.

The mutations of bacteria due to the excessive use of antibiotics, and generation of antibiotic-resistant bacteria have made the development of new antibacterial compounds a necessity. MXenes have emerged as biocompatible transition metal carbide structures with extensive biomedical applications. This is related to the MXenes' unique combination of properties, including multifarious elemental compositions, 2D-layered structure, large surface area, abundant surface terminations, and excellent photothermal and photoelectronic properties. The focus of this review is the antibacterial application of MXenes, which has attracted the attention of researchers since 2016. A quick overview of the synthesis strategies of MXenes is provided and then summarizes the effect of various factors (including structural properties, optical properties, surface charges, flake size, and dispersibility) on the biocidal activity of MXenes. The main mechanisms for deactivating bacteria by MXenes are discussed in detail including rupturing of the bacterial membrane by sharp edges of MXenes nanoflakes, generating the reactive oxygen species (ROS), and photothermal deactivating of bacteria. Hybridization of MXenes with other organic and inorganic materials can result in materials with improved biocidal activities for different applications such as wound dressings and water purification. Finally, the challenges and perspectives of MXene nanomaterials as biocidal agents are presented.

Design of Atomic Ordering in Mo2Nb2C3Tx MXenes for Hydrogen Evolution Electrocatalysis.

The need for novel materials for energy storage and generation calls for chemical control at the atomic scale in nanomaterials. Ordered double-transition-metal MXenes expanded the chemical diversity of the family of atomically layered 2D materials since their discovery in 2015. However, atomistic tunability of ordered MXenes to achieve ideal composition-property relationships has not been yet possible. In this study, we demonstrate the synthesis of Mo2+αNb2-αAlC3 MAX phases (0 ≤ α ≤ 0.3) and confirm the preferential ordering behavior of Mo and Nb in the outer and inner M layers, respectively, using density functional theory, Rietveld refinement, and electron microscopy methods. We also synthesize their 2D derivative Mo2+αNb2-αC3Tx MXenes and exemplify the effect of preferential ordering on their hydrogen evolution reaction electrocatalytic behavior. This study seeks to inspire further exploration of the ordered double-transition-metal MXene family and contribute composition-behavior tools toward application-driven design of 2D materials.

Perspectives of 2D MXene Tribology.

The large and rapidly growing family of 2D early transition metal carbides, nitrides, and carbonitrides (MXenes) raises significant interest in the materials science and chemistry of materials communities. Discovered a little more than a decade ago, MXenes have already demonstrated outstanding potential in various applications ranging from energy storage to biology and medicine. The past two years have witnessed increased experimental and theoretical efforts toward studying MXenes' mechanical and tribological properties when used as lubricant additives, reinforcement phases in composites, or solid lubricant coatings. Although research on the understanding of the friction and wear performance of MXenes under dry and lubricated conditions is still in its early stages, it has experienced rapid growth due to the excellent mechanical properties and chemical reactivities offered by MXenes that make them adaptable to being combined with other materials, thus boosting their tribological performance. In this perspective, the most promising results in the area of MXene tribology are summarized, future important problems to be pursued further are outlined, and methodological recommendations that could be useful for experts as well as newcomers to MXenes research, in particular, to the emerging area of MXene tribology, are provided.

Spherical Templating of CoSe2 Nanoparticle-Decorated MXenes for Lithium-Sulfur Batteries.

Two-dimensional MXenes produce competitive performances when incorporated into lithium-sulfur batteries (LSBs), solving key problems such as the poor electronic conductivity of sulfur and dissolution of its polysulfide intermediates. However, MXene nanosheets are known to easily aggregate and restack during electrode fabrication, filtration, or water removal, limiting their practical applicability. Furthermore, in complex electrocatalytic reactions like the multistep sulfur reduction process in LSBs, MXene alone is insufficient to ensure an optimal reaction pathway. In this work, we demonstrate for the first time a loose templating of sulfur spheres using Ti3C2Tx MXene nanosheets decorated with polymorphic CoSe2 nanoparticles. This work shows that the templating of sulfur spheres using nanoparticle-decorated MXene nanosheets can prevent nanosheet aggregation and exert a strong electrocatalytic effect, thereby enabling improved reaction kinetics and battery performance. The S@MXene-CoSe2 cathode demonstrated a long cycle life of 1000 cycles and a low capacity decay rate of 0.06% per cycle in LSBs.

Nanoscale MXene Interlayer and Substrate Adhesion for Lubrication: A Density Functional Theory Study.

Understanding the interlayer interaction at the nanoscale in two-dimensional (2D) transition metal carbides and nitrides (MXenes) is important to improve their exfoliation/delamination process and application in (nano)-tribology. The layer-substrate interaction is also essential in (nano)-tribology as effective solid lubricants should be resistant against peeling-off during rubbing. Previous computational studies considered MXenes' interlayer coupling with oversimplified, homogeneous terminations while neglecting the interaction with underlying substrates. In our study, Ti-based MXenes with both homogeneous and mixed terminations are modeled using density functional theory (DFT). An ad hoc modified dispersion correction scheme is used, capable of reproducing the results obtained from a higher level of theory. The nature of the interlayer interactions, comprising van der Waals, dipole-dipole, and hydrogen bonding, is discussed along with the effects of MXene sheet's thickness and C/N ratio. Our results demonstrate that terminations play a major role in regulating MXenes' interlayer and substrate adhesion to iron and iron oxide and, therefore, lubrication, which is also affected by an external load. Using graphene and MoS2 as established references, we verify that MXenes' tribological performance as solid lubricants can be significantly improved by avoiding -OH and -F terminations, which can be done by controlling terminations via post-synthesis processing.

Ti3C2Tx MXene Polymer Composites for Anticorrosion: An Overview and Perspective.

As the most studied two-dimensional (2D) material from the MXene family, Ti3C2Tx has constantly gained interest from academia and industry. Ti3C2Tx MXene has the highest electrical conductivity (up to 24,000 S cm-1) and one of the highest stiffness values with a Young's modulus of ∼ 334 GPa among water-dispersible conductive 2D materials. The negative surface charge of MXene helps to disperse it well in aqueous and other polar solvents. This solubility across a wide range of solvents, excellent interface interaction, tunable surface functionality, and stability with other organic/polymeric materials combined with the layered structure of Ti3C2Tx MXene make it a promising material for anticorrosion coatings. While there are many reviews on Ti3C2Tx MXene polymer composites for catalysis, flexible electronics, and energy storage, to our knowledge, no review has been published yet on MXenes' anticorrosion applications. In this brief report, we summarize the current progress and the development of Ti3C2Tx polymer composites for anticorrosion. We also provide an outlook and discussion on possible ways to improve the exploitation of Ti3C2Tx polymer composites as anticorrosive materials. Finally, we provide a perspective beyond Ti3C2Tx MXene composition for the development of future anticorrosion coatings.

Electrically conductive 3D printed Ti3C2Tx MXene-PEG composite constructs for cardiac tissue engineering.

Tissue engineered cardiac patches have great potential as a therapeutic treatment for myocardial infarction (MI). However, for successful integration with the native tissue and proper function of the cells comprising the patch, it is crucial for these patches to mimic the ordered structure of the native extracellular matrix and the electroconductivity of the human heart. In this study, a new composite construct that can provide both conductive and topographical cues for human induced pluripotent stem cell derived cardiomyocytes (iCMs) is developed for cardiac tissue engineering applications. The constructs are fabricated by 3D printing conductive titanium carbide (Ti3C2Tx) MXene in pre-designed patterns on polyethylene glycol (PEG) hydrogels, using aerosol jet printing, at a cell-level resolution and then seeded with iCMs and cultured for one week with no signs of cytotoxicity. The results presented in this work illustrate the vital role of 3D-printed Ti3C2Tx MXene on aligning iCMs with a significant increase in MYH7, SERCA2, and TNNT2 expressions, and with an improved synchronous beating as well as conduction velocity. This study demonstrates that 3D printed Ti3C2Tx MXene can potentially be used to create physiologically relevant cardiac patches for the treatment of MI. STATEMENT OF SIGNIFICANCE: As cardiovascular diseases and specifically myocardial infarction (MI) continue to be the leading cause of death worldwide, it is critical that new clinical interventions be developed. Tissue engineered cardiac patches have shown significant potential as clinical therapeutics to promote recovery following MI. Unfortunately, current constructs lack the ordered structure and electroconductivity of native human heart. In this study, we engineered a composite construct that can provide both conductive and topographical cues for human induced pluripotent stem cell derived cardiomyocytes. By 3D printing conductive Ti3C2Tx MXene in pre-designed patterns on polyethylene glycol hydrogels, using aerosol jet printing, at a cell-level resolution, we developed tissue engineered patches that have the potential for providing a new clinical therapeutic to combat cardiovascular disease.

Covalent Surface Modification of Ti3C2Tx MXene with Chemically Active Polymeric Ligands Producing Highly Conductive and Ordered Microstructure Films.

As interest continues to grow in Ti3C2Tx and other related MXenes, advancement in methods of manipulation of their surface functional groups beyond synthesis-based surface terminations (Tx: -F, -OH, and ═O) can provide mechanisms to enhance solution processability as well as produce improved solid-state device architectures and coatings. Here, we report a chemically important surface modification approach in which "solvent-like" polymers, polyethylene glycol carboxylic acid (PEG6-COOH), are covalently attached onto MXenes via esterification chemistry. Surface modification of Ti3C2Tx with PEG6-COOH with large ligand loading (up to 14% by mass) greatly enhances dispersibility in a wide range of nonpolar organic solvents (e.g., 2.88 mg/mL in chloroform) without oxidation of Ti3C2Tx two-dimensional flakes or changes in the structure ordering. Furthermore, cooperative interactions between polymer chains improve the nanoscale assembly of uniform microstructures of stacked MXene-PEG6 flakes into ordered thin films with excellent electrical conductivity (∼16,200 S·cm-1). Most importantly, our covalent surface modification approach with ω-functionalized PEG6 ligands (ω-PEG6-COOH, where ω: -NH2, -N3, -CH═CH2) allows for control over the degree of functionalization (incorporation of valency) of MXene. We believe that installing valency onto MXenes through short, ion conducting PEG ligands without compromising MXenes' features such as solution processability, structural stability, and electrical conductivity further enhance MXenes surface chemistry tunability and performance and widens their applications.

Nacre-Mimetic, Mechanically Flexible, and Electrically Conductive Silk Fibroin-MXene Composite Foams as Piezoresistive Pressure Sensors.

The hierarchical nacre-like three-dimensional (3D) assembly of porous and lightweight materials is in high demand for applications such as sensors, flexible energy storage and harvesting devices, electromagnetic interference shielding, and biomedical applications. However, designing such a biomimetic hierarchical architecture is highly challenging due to the lack of experimental approaches to achieve the necessary control over the materials' microstructure on the multilength scale. Aerogels and foam-based materials have recently been developed as attractive candidates for pressure-sensing applications. However, despite recent progress, the bottleneck for these materials to achieve electrical conductivity combined with high mechanical flexibility and fast strain recovery remains. In this study, for the first time, inspired by the multiscale architecture of nacre, we fabricated a series of ultra-lightweight, flexible, electrically conductive, and relatively high-strength composite foams through hybridizing the cross-linked silk fibroin (SF) biopolymer, extracted from Bombyx mori silkworm cocoon, reinforced with two-dimensional graphene oxide (GO) and Ti3C2 MXene nanosheets. Nacre is a naturally porous material with a lightweight, mechanically robust network structure, thanks to its 3D interconnected lamella-bridge micromorphology. Inspired by this material, we assemble a cross-linked SF fibrous solution with MXene and GO nanosheets into nacre-like architecture using a bidirectional freeze-casting technique. Subsequent freeze-drying and gas-phase hydrophobization resulted in composite foams with 3D hierarchical porous architectures with a unique combination of mechanical resilience, electrical conductance, and ultra-lightness. The developed composite presented excellent performances as piezoresistive pressure-sensing devices and sorbents for oil/water separation, which indicated great potential in mechanically switchable electronics.

High-Entropy 2D Carbide MXenes: TiVNbMoC3 and TiVCrMoC3.

Two-dimensional (2D) transition metal carbides and nitrides, known as MXenes, are a fast-growing family of 2D materials. MXenes 2D flakes have n + 1 (n = 1-4) atomic layers of transition metals interleaved by carbon/nitrogen layers, but to-date remain limited in composition to one or two transition metals. In this study, by implementing four transition metals, we report the synthesis of multi-principal-element high-entropy M4C3Tx MXenes. Specifically, we introduce two high-entropy MXenes, TiVNbMoC3Tx and TiVCrMoC3Tx, as well as their precursor TiVNbMoAlC3 and TiVCrMoAlC3 high-entropy MAX phases. We used a combination of real and reciprocal space characterization (X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, and scanning transmission electron microscopy) to establish the structure, phase purity, and equimolar distribution of the four transition metals in high-entropy MAX and MXene phases. We use first-principles calculations to compute the formation energies and explore synthesizability of these high-entropy MAX phases. We also show that when three transition metals are used instead of four, under similar synthesis conditions to those of the four-transition-metal MAX phase, two different MAX phases can be formed (i.e., no pure single-phase forms). This finding indicates the importance of configurational entropy in stabilizing the desired single-phase high-entropy MAX over multiphases of MAX, which is essential for the synthesis of phase-pure high-entropy MXenes. The synthesis of high-entropy MXenes significantly expands the compositional variety of the MXene family to further tune their properties, including electronic, magnetic, electrochemical, catalytic, high temperature stability, and mechanical behavior.