Synthesis of Hydrofluoric (HF) Acid Free, Two-Dimensional (2D) Tantalum Carbide MXene Nanosheets and Quantum Dots.

MXenes are two-dimensional (2D) transition metal-based carbides, nitrides, and carbonitrides that are synthesized from its precursor MAX phase. The selective etching of the "A" from the MAX phase yields multi-functional MXenes that hold promise in a wide range of energy-based applications and biomedical applications. Based on its intended application, MXenes are prepared as multilayered sheets, monolayer flakes, and quantum dots. Conventionally, MXenes are prepared using hydrofluoric (HF) acid etching; however, the use of HF impedes its effective use in biomedical applications. This calls for the use of nontoxic HF-free synthesis protocols to prepare MXenes safe for biological use. Therefore, we have discussed a facile process to synthesize biocompatible, HF-free MXene nanosheets and quantum dots.

Recent Progress in the Applications of MXene-Based Materials in Multivalent Ion Batteries.

Multivalent-ion batteries have garnered significant attention as promising alternatives to traditional lithium-ion batteries due to their higher charge density and potential for sustainable energy storage solutions. Nevertheless, the slow diffusion of multivalent ions is the primary issue with electrode materials for multivalent-ion batteries. In this review, the suitability of MXene-based materials for multivalent-ion batteries applications is explored, focusing onions such as magnesium (Mg2+), aluminum (Al3+), zinc (Zn2+), and beyond. The unique structure of MXene offers large interlayer spacing and abundant surface functional groups that facilitates efficient ion intercalation and diffusion, making it an excellent candidate for multivalent-ion batteries electrodes with excellent specific capacity and power density. The latest advancements in MXene synthesis and engineering techniques to enhance its electrochemical performance have been summarized and discussed. With the versatility of MXenes and their ability to harness diverse multivalent ions, this review underscores the promising future of MXene-based materials in revolutionizing the landscape of multivalent-ion batteries.

Hybridization of metal-organic frameworks and MXenes: Expanding horizons in supercapacitor applications.

Metal-organic frameworks (MOFs) and MXenes have gained prominence in the queue of advanced material research. Both materials' outstanding physical and chemical characteristics prominently promote their utilization in diverse fields, especially the electrochemical energy storage (EES) domain. The collective contribution of extremely high specific surface area (SSA), customizable pores, and abundant active sites propose MOFs as integral materials for EES devices. However, conventional MOFs endure low conductivity, constraining their utility in practical applications. The development of hybrid materials via integrating MOFs with various conductive materials stands out as an effective approach to improvising MOF's conductivity. MXenes, formulated as two-dimensional (2D) carbides and nitrides of transition metals, fall in the category of the latest 2D materials. MXenes possess extensive structural diversity, impressive conductivity, and rich surface chemical characteristics. The electrochemical characteristics of MOF@MXene hybrids outperform MOFs and MXenes individually, credited to the synergistic effect of both components. Additionally, the MOF derivatives coupled with MXene, exhibiting unique morphologies, demonstrate outstanding electrochemical performance. The important attributes of MOF@MXene hybrids, including the various synthesis protocols, have been summarized in this review. This review delves into the architectural analysis of both MOFs and MXenes, along with their advanced hybrids. Furthermore, the comprehensive survey of the latest advancements in MOF@MXene hybrids as electroactive material for supercapacitors (SCs) is the prime objective of this review. The review concludes with an elaborate discussion of the current challenges faced and the future outlooks for optimizing MOF@MXene composites.

Tailoring Alkalized and Oxidized V2CTx as Anode Materials for High-Performance Lithium Ion Batteries.

V2CTx MXenes have gained considerable attention in lithium ion batteries (LIBs) owing to their special two-dimensional (2D) construction with large lithium storage capability. However, engineering high-capacity V2CTx MXenes is still a great challenge due to the limited interlayer space and poor surface terminations. In view of this, alkalized and oxidized V2CTx MXenes (OA-V2C) are envisaged. SEM characterization confirms the accordion-like layered morphology of OA-V2C. The XPS technique illustrates that undergoing alkalized and oxidized treatment, V2CTX MXene replaces -F and -OH with -O groups, which are more conducive to pseudocapacitive properties as well as Na ion diffusion, providing more active sites for ion storage in OA-V2C. Accordingly, the electrochemical performance of OA-V2C as anode materials for LIBs is evaluated in this work, showing excellent performance with high reversible capacity (601 mAh g-1 at 0.2 A g-1 over 500 cycles), competitive rate performance (222.2 mAh g-1 and 152.8 mAh g-1 at 2 A g-1 and 5 A g-1), as well as durable long-term cycling property (252 mAh g-1 at 5 A g-1 undergoing 5000 cycles). It is noted that the intercalation of Na+ ions and oxidation co-modification greatly reduces F surface termination and concurrently increases interlayer spacing in OA-V2C, significantly expediting ion/electron transportation and providing an efficient way to maximize the performance of MXenes in LIBs. This innovative refinement methodology paves the way for building high-performance V2CTx MXenes anode materials in LIBs.

2D MXene-Based Nanoscale Materials for Electrochemical Sensing Toward the Detection of Hazardous Pollutants: A Perspective.

MXenes (Mn+1XnTx), a subgroup of 2-dimensional (2D) materials, specifically comprise transition metal carbides, nitrides, and carbonitrides. They exhibit exceptional electrocatalytic and photocatalytic properties, making them well-suited for the detection and removal of pollutants from aqueous environments. Because of their high surface area and remarkable properties, they are being utilized in various applications, including catalysis, sensing, and adsorption, to combat pollution and mitigate its adverse effects. Different characterization techniques like XRD, SEM, TEM, UV-Visible spectroscopy, and Raman spectroscopy have been used for the structural elucidation of 2D MXene. Current responses against applied potential were measured during the electrochemical sensing of the hazardous pollutants in an aqueous system using a variety of electroanalytical techniques, including differential pulse voltammetry, amperometry, square wave anodic stripping voltammetry, etc. In this review, a comprehensive discussion on structural patterns, synthesis, properties of MXene and their application for electrochemical detection of lethal pollutants like hydroquionone, phenol, catechol, mercury and lead, etc. are presented. This review will be helpful to critically understand the methods of synthesis and application of MXenes for the removal of environmental pollutants.

Advances in MXene-based technologies for the remediation of toxic phenols: A comprehensive review.

The pressing global issue of organic pollutants, particularly phenolic compounds derived primarily from industrial wastes, poses a significant threat to the environment. Although progress has been made in the development of low-cost materials for phenolic compound removal, their effectiveness remains limited. Thus, there is an urgent need for novel technologies to comprehensively address this issue. In this context, MXenes, known for their exceptional physicochemical properties, have emerged as highly promising candidates for the remediation of phenolic pollutants. This review aims to provide a comprehensive and critical evaluation of MXene-based technologies for the removal of phenolic pollutants, focusing on the following key aspects: (1) The classification and categorization of phenolic pollutants, highlighting their adverse environmental impacts, and emphasizing the crucial need for their removal. (2) An in-depth discussion on the synthesis methods and properties of MXene-based composites, emphasizing their suitability for environmental remediation. (3) A detailed analysis of MXene-based adsorption, catalysis, photocatalysis, and hybrid processes, showcasing current advancements in MXene modification and functionalization to enhance removal efficiency. (4) A thorough examination of the removal mechanisms and stability of MXene-based technologies, elucidating their operating conditions and stability in pollutant removal scenarios. (5) Finally, this review concludes by outlining future challenges and opportunities for MXene-based technologies in water treatment, facilitating their potential applications. This comprehensive review provides valuable insights and innovative ideas for the development of versatile MXene-based technologies tailored to combat water pollution effectively.

All-MXene electronic tongue for neurotransmitters detection.

Neurotransmitters (NTs) are molecules produced by neurons that act as the body's chemical messengers. Their abnormal levels in the human system have been associated with many disorders and neurodegenerative diseases, which makes the monitoring of NTs fundamentally important. Specifically for clinical analysis and understanding of brain behavior, simultaneous detection of NTs at low levels quickly and reliably is imperative for disease prevention and early diagnosis. However, the methods currently employed are usually invasive or inappropriate for multiple NTs detection. Herein, we developed a MXene-based impedimetric electronic tongue (e-tongue) for sensitive NT monitoring, using Nb2C, Nb4C3, Mo2C, and Mo2Ti2C3 MXenes as sensing units of the e-tongue, and Principal Component Analysis (PCA) as the data treatment method. The high specific surface area, distinct electrical properties, and chemical stability of the MXenes gave rise to high sensitivity and good reproducibility of the sensor array toward NT detection. Specifically, the e-tongue detected and differentiated multiple NTs (acetylcholine, dopamine, glycine, glutamate, histamine, and tyrosine) at concentrations as low as 1 nmol L-1 and quantified NTs present in a mixture. Besides, analyses performed with interferents and actual samples confirmed the system's potential to be used in clinical diagnostics. The results demonstrate that the MXene-based e-tongue is a suitable, rapid, and simple method for NT monitoring with high accuracy and sensitivity.

Aptamer-Functionalized Magnetic Ti3C2 Based Nanoplatform for Simultaneous Enrichment and Detection of Exosomes.

Exosomes are nanovesicles secreted by cells, which play a crucial role in various pathological processes. Exosomes have shown great promise as tumor biomarkers because of the abundant secretion during tumor formation. The development of a convenient, efficient, and cost-effective method for simultaneously enriching and detecting exosomes is of utmost importance for both basic research and clinical applications. In this study, an aptamer-functionalized magnetic Ti3C2 composite material (Fe3O4@Ti3C2@PEI@DSP@aptamer@FAM-ssDNA) is prepared for the simultaneous enrichment and detection of exosomes. CD63 aptamers are utilized to recognize and capture the exosomes, followed by magnetic separation. The exosomes are then released by cleaving the disulfide bonds of DSP. Compared to traditional methods, Fe3O4@Ti3C2@PEI@DSP@aptamer@FAM-ssDNA exhibited superior efficiency in enriching exosomes while preserving their structural and functional integrity. Detection of exosome concentration is achieved through the fluorescence quenching of Ti3C2 and the competitive binding between the exosomes and a fluorescently labeled probe. This method exhibited a low detection limit of 4.21 × 104 particles mL-1, a number that is comparable to the state-of-the-art method in the detection of exosomes. The present study demonstrates a method of simultaneous enrichment and detection of exosomes with a high sensitivity, accuracy, specificity, and cost-effectiveness providing significant potential for clinical research and diagnosis.

A novel electrochemical sensor for detection of luteolin in food based on 3D networked electrically interconnected SiO2@GO/MXene composite.

Luteolin (Lu), a compound with various biochemical and pharmacological activities beneficial to human health, has attracted researchers' attention. This study proposes an efficient and scalable method using ultrasound to intercalate graphene oxide (GO)-coated silica spheres (SiO2) into MXenes, resulting in a 3D conductive interconnected structural composite material. Characterization of the composite material was conducted using SEM, TEM, XRD, XPS, and Raman spectroscopy. MXenes exhibit excellent electrical conductivity, and the SiO2@GO surface with abundant hydroxyl and silanol groups provides high-binding active sites that facilitate Lu molecule enrichment. The formation of the 3D conductive interconnected structural composites enhances charge transport, significantly improving sensor sensitivity. Consequently, the sensor demonstrates excellent detection capabilities (detection range 0.03-7000 nM, detection limit 12 pM). Furthermore, the sensor can be applied to quantitative determination of Lu in real samples, including chrysanthemums, Jiaduobao, honeysuckle, purple perilla, and peanut shells, achieving recoveries between 98.2 and 104.7%.

Evolution of Surface Chemistry in Two-Dimensional MXenes: From Mixed to Tunable Uniform Terminations.

Surface chemistry of MXenes is of great interest as the terminations can define the intrinsic properties of this family of materials. The diverse and tunable terminations also distinguish MXenes from many other 2D materials. Conventional fluoride-containing reagents etching approaches resulted in MXenes with mixed fluoro-, oxo-, and hydroxyl surface groups. The relatively strong chemical bonding of MXenes' surface metal atoms with oxygen and fluorine makes post-synthetic covalent surface modifications of such MXenes unfavorable. In this minireview, we focus on the recent advances in MXenes with uniform surface terminations. Unconventional methods, including Lewis acidic molten salt etching (LAMS) and bottom-up direct synthesis, have been proven successful in producing halide-terminated MXenes. These synthetic strategies have opened new possibilities for MXenes because weaker surface chemical bonds in halide-terminated MXenes facilitate post-synthetic covalent surface modifications. Both computational and experimental results on surface termination-dependent properties are summarized and discussed. Finally, we offer our perspective on the opportunities and challenges in this exciting research field.

Modulating Electrochemical Energy Storage and Multi-Spectra Defense of MXenes by Interfacial Dual-Filler Engineering.

MXenes have attracted growing interest in electrochemical energy storage owing to their high electronic conductivity and editable surface chemistry. Besides, rendering MXenes with spectrum defense properties further broadens their versatile applications. However, the development of MXenes suffers from weak van der Waal interaction-driven self-restacking that leads to random alignment and inferior interface microenvironments. Herein, a nacre-inspired MXene film is tailored by dual-filling of 2-ureido-4[1H]-pyrimidinone (UPy)-modified polyvinyl alcohol (PVA-UPy) and carbon nanotubes (CNTs). The dual-nanofillers engineering endows the nanocomposite film with a highly ordered structure (a Herman's order value of 0.838), a high mechanical strength (139.5 MPa), and continuous conductive pathways of both the ab plane and c-axis. As a proof-of-concept, the tailored nanocomposite film achieves a considerable capacitance of 508.2 F cm-3 and long-term cycling stability without performance degradation for 10 000 cycles. It is efficient for spectra defense in radar and infrared bands, displaying a high electromagnetic shielding capacity (19186 dB cm2 g-1) and a super-low infrared (IR) emissivity (0.16), with negligible performance decay after saving in the air for 1 year, responsible for the applications in specific and complex conditions. This interfacial dual-filler engineering concept showcases effective nanotechnology toward sustainable energy applications with a long lifetime and safety.

Nanoscale Surface and Bulk Electronic Properties of Ti3C2Tx MXene Unraveled by Multimodal X-Ray Spectromicroscopy.

2D layered materials, such as transition metal carbides or nitrides, known as MXenes, offer an ideal platform to investigate charge transfer processes in confined environment, relevant for energy conversion and storage applications. Their rich surface chemistry plays an essential role in the pseudocapacitive behavior of MXenes. However, the local distribution of surface functional groups over single flakes and within few- or multilayered flakes remains unclear. In this work, scanning X-ray microscopy (SXM) is introduced with simultaneous transmission and electron yield detection, enabling multimodal nanoscale chemical imaging with bulk and surface sensitivity, respectively, of individual MXene flakes. The Ti chemical bonding environment is found to significantly vary between few-layered hydrofluoric acid-etched Ti3C2Tx MXenes and multilayered molten salt (MS)-etched Ti3C2Tx MXenes. Postmortem analysis of MS-etched Ti3C2Tx electrodes cycled in a Li-ion battery further illustrates that simultaneous bulk and surface chemical imaging using SXM offers a method well adapted to the characterization of the electrode-electrolyte interactions at the nanoscale.

Recent Advances in Non-Ti MXenes: Synthesis, Properties, and Novel Applications.

One of the most fascinating 2D nanomaterials (NMs) ever found is various members of MXene family. Among them, the titanium-based MXenes, with more than 70% of publication-related investigations, are comparatively well studied, producing fundamental foundation for the 2D MXene family members with flexible properties, familiar with a variety of advanced novel technological applications. Nonetheless, there are still more candidates among transitional metals (TMs) that can function as MXene NMs in ways that go well beyond those that are now recognized. Systematized details of the preparations, characteristics, limitations, significant discoveries, and uses of the novel M-based MXenes (M-MXenes), where M stands for non-Ti TMs (M = Sc, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W, and Lu), are given. The exceptional qualities of the 2D non-Ti MXene outperform standard Ti-MXene in several applications. There is many advancement in top-down as well as bottom-up production of MXenes family members, which allows for exact control of the M-characteristics MXene NMs to contain cutting-edge applications. This study offers a systematic evaluation of existing research, covering everything in producing complex M-MXenes from primary limitations to the characterization and selection of their applications in accordance with their novel features. The development of double metal combinations, extension of additional metal candidates beyond group-(III-VI)B family, and subsequent development of the 2D TM carbide/TMs nitride/TM carbonitrides to 2D metal boride family are also included in this overview. The possibilities and further recommendations for the way of non-Ti MXene NMs are in the synthesis of NMs will discuss in detail in this critical evaluation.

Electrochemical Stability of MXenes in Water Based on Constant Potential AIMD Simulations.

MXene has been recently explored as promising electrocatalytic materials to accelerate the electrocatalytic process for hydrogen evolution, but their dynamic stability under electrochemical conditions remains elusive. Here we performed first-principle ab initio molecular dynamics calculations to reveal the electrochemical stability of Ti2CTx MXene in different aqueous environments. The results revealed the high vulnerability of the pure and vacancy-defected Ti2CO2 MXene towards water attack, leading to surface oxidation of MXene under neutral electrochemical condition that formed adsorbed oxygen species to Ti and dissociated proton in solution. The surface oxidation of Ti2CO2 could be prevented in the acid condition or in the neutral condition under the negative potential. Differently, the fully F- or OH-functionalized Ti2CF2 and Ti2C(OH)2 as well as the mixed functionalized Ti2C(O0.5OH0.5)2 and Ti2CO1.12F0.88 are highly stable under various electrochemical conditions, which can effectively prevent close contact between water and surface Ti atoms via electronic repulsion or steric hindrance. These findings provide atomic level understanding of the aqueous stability of MXene and provide useful strategies to prevent degradation and achieve highly stable MXenes.

MXenes and MXene-Based Metal Hydrides for Solid-State Hydrogen Storage: A Review.

Hydrogen-driven energy is fascinating among the everlasting energy sources, particularly for stationary and onboard transportation applications. Efficient hydrogen storage presents a key challenge to accomplishing the sustainability goals of hydrogen economy. In this regard, solid-state hydrogen storage in nanomaterials, either physically or chemically adsorbed, has been considered a safe path to establishing sustainability goals. Though metal hydrides have been extensively explored, they fail to comply with the set targets for practical utilization. Recently, MXenes, both in bare form and hybrid state with metal hydrides, have proven their flair in ascertaining the hydrides' theoretical and experimental hydrogen storage capabilities far beyond the fancy materials and current state-of-the-art technologies. This review encompasses the significant accomplishments achieved by MXenes (primarily in 2019-2024) for enhancing the hydrogen storage performance of various metal hydride materials such as MgH2, AlH3, Mg(BH4)2, LiBH4, alanates, and composite hydrides. It also discusses the bottlenecks of metal hydrides for hydrogen storage, the potential use of MXenes hybrids, and their challenges, such as reversibility, H2 losses, slow kinetics, and thermodynamic barriers. Finally, it concludes with a detailed roadmap and recommendations for mechanistic-driven future studies propelling toward a breakthrough in solid material-driven hydrogen storage using cost-effective, efficient, and long-lasting solutions.

A review of etching methods and applications of two-dimensional MXenes.

MXenes have been attracting much attention since their introduction due to their amazing properties such as unique structure, good hydrophilicity, metal-grade electrical conductivity, rich surface chemistry, low ionic diffusion resistance, and excellent mechanical strength. It is noteworthy that different synthesis methods have a great influence on the structure and properties of MXenes. In recent years, some modification strategies of MXenes with unique insights have been developed with the increasing research. In summary, this paper reviews and summarizes the recent research progress of MXenes from the perspective of preparation processes (including hydrofluoric acid direct etching, fluoride/concentrated acid hybrid etching, fluoride melt etching, electrochemical etching, alkali-assisted etching and Lewis acid etching strategies), which can provide valuable guidance for the preparation and application of high-performance MXenes-based materials.

Theoretical Study of Catalytic Performance of Pristine M2C and Oxygen-Functionalized M2CO2 MXenes as Cathodes for Li-N2 Batteries.

Li-N2 batteries are a promising platform for electrochemical energy storage, but their performance is limited by the low activity of the cathode catalysts. In this work, density functional theory was used to study the catalytic activity of the pristine M2C and oxygen-functionalized M2CO2 MXenes (M = Sc, Ti, and V) as cathodes for Li-N2 batteries. The calculated results suggest that the pristine M2C MXenes (M = Sc, Ti, and V) show high electrical conductivity due to the Fermi level crossing the metal 3d states. The stable adsorption of N2 occurs on M2C MXenes via a side-on model and strengthens gradually with decreasing metal atomic number. Furthermore, the kinetics of N2 dissociation can be significantly accelerated by the coadsorption of Li on M2C MXenes. However, adsorption and dissociation of N2 on the M2CO2 surfaces are too difficult to occur due to strong electrostatic repulsion. The Li-mediated nitrogen reduction reaction during discharge proceeds favorably via (N + N)* → (LiN + N)* → (LiN + LiN)* → (Li2N + LiN)* → (Li2N + Li2N)* → (Li3N + Li2N)* → (Li3N + Li3N)* to form two isolated Li3N* on M2C MXenes. The calculated charge-discharge overpotentials decrease in the order of Sc2C < Ti2C < V2C. Notably, the Sc2C MXene has great potential as a cathode catalyst for Li-N2 batteries because of its high electrical conductivity, strong N2 adsorption, favorable Li-mediated N2 dissociation, and ultralow discharging, charging, and total overpotentials (0.07, 0.06, and 0.13 V). This study offers a theoretical foundation for future research on Li-N2 batteries.

Covalent Bonding of MXene/COF Heterojunction for Ultralong Cycling Li-Ion Battery Electrodes.

Covalent organic frameworks (COFs) have emerged as promising renewable electrode materials for LIBs and gained significant attention, but their capacity has been limited by the densely packed 2D layer structures, low active site availability, and poor electronic conductivity. Combining COFs with high-conductivity MXenes is an effective strategy to enhance their electrochemical performance. Nevertheless, simply gluing them without conformal growth and covalent linkage restricts the number of redox-active sites and the structural stability of the composite. Therefore, in this study, a covalently assembled 3D COF on Ti3C2 MXenes (Ti3C2@COF) is synthesized and serves as an ultralong cycling electrode material for LIBs. Due to the covalent bonding between the COF and Ti3C2, the Ti3C2@COF composite exhibits excellent stability, good conductivity, and a unique 3D cavity structure that enables stable Li+ storage and rapid ion transport. As a result, the Ti3C2-supported 3D COF nanosheets deliver a high specific capacity of 490 mAh g-1 at 0.1 A g-1, along with an ultralong cyclability of 10,000 cycles at 1 A g-1. This work may inspire a wide range of 3D COF designs for high-performance electrode materials.

Functional group induced transformations in stacking and electron structure in Mo2CTx/NiS heterostructures.

The two-dimensional transition metal carbide/nitride family (MXenes) has garnered significant attention due to their highly customizable surface functional groups. Leveraging modern material science techniques, the customizability of MXenes can be enhanced further through the construction of associated heterostructures. As indicated by recent research, the Mo2CTx/NiS heterostructure has emerged as a promising candidate exhibiting superior physical and chemical application potential. The geometrical structure of Mo2CTx/NiS heterostructure is modeled and six possible configurations are validated by Density Functional Theory simulations. The variation in functional groups leads to structural changes in Mo2CTx/NiS interfaces, primarily attributed to the competition between van der Waals and covalent interactions. The presence of different functional groups results in significant band fluctuations near the Fermi level for Ni and Mo atoms, influencing the role of atoms and electron's ability to escape near the interface. This, in turn, modulates the strength of covalent interactions at the MXenes/NiS interface and alters the ease of dissociation of the MXenes/NiS complex. Notably, the Mo2CO2/NiS(P63/mmc) heterostructure exhibits polymorphism, signifying that two atomic arrangements can stabilize the structure. The transition process between these polymorphs is also simulated, further indicating the modulation of the electronic level of properties by a sliding operation.

M4X3 MXenes: Application in Energy Storage Devices.

MXene has garnered widespread recognition in the scientific community due to its remarkable properties, including excellent thermal stability, high conductivity, good hydrophilicity and dispersibility, easy processability, tunable surface properties, and admirable flexibility. MXenes have been categorized into different families based on the number of M and X layers in Mn+1Xn, such as M2X, M3X2, M4X3, and, recently, M5X4. Among these families, M2X and M3X2, particularly Ti3C2, have been greatly explored while limited studies have been given to M5X4 MXene synthesis. Meanwhile, studies on the M4X3 MXene family have developed recently, hence, demanding a compilation of evaluated studies. Herein, this review provides a systematic overview of the latest advancements in M4X3 MXenes, focusing on their properties and applications in energy storage devices. The objective of this review is to provide guidance to researchers on fostering M4X3 MXene-based nanomaterials, not only for energy storage devices but also for broader applications.