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            Abstract M5X4MXenes, a subclass of 2D transition metal carbides, have attracted attention as the thickest 2D material synthesized. Early studies show their promising electrocatalytic activity but overlooked how metal composition and interlayer spacing affect hydrogen evolution reaction (HER). To address this gap, three M5X4MXenes, Mo4VC4, (TiTa)5C4, and (TiNb)5C4, are systematically studied and their interlayer spacing and composition modulated through ion exchange with tetramethyl ammonium (TMA+vs. Li+), providing new insights into their HER activity. These findings reveal that TMA+‐intercalated Mo4VC4exhibits superior HER activity, achieving areal and gravimetric overpotentials of 172 and 90 mV, respectively, due to its composition (presence of Mo) and expanded interlayer spacing that enhances proton accessibility. The Li+exchange increases the overpotential to 212 and 131 mV at 10 mA areal and gravimetric current density, respectively, as reduced interlayer spacing restricts access to active Mo sites. In contrast, (TiNb)5C4and (TiTa)5C4display higher overpotentials, making them more suitable for supercapacitor or aqueous battery applications due to the wider electrochemical window. This study provides critical insights into the interplay between metal composition and interlayer engineering in M5X4MXenes, establishing TMA‐Mo4VC4as a promising candidate for sustainable hydrogen production.more » « lessFree, publicly-accessible full text available July 23, 2026
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            Abstract MXene‐based nanozymes (recently called MXenzymes) have emerged as promising candidates for environmental remediation, biomedical, (bio‐)catalytic, and sensing technologies due to their surface tunability, tailored electronic properties, remarkable electrical conductivity, and high surface area. These materials offer significant advantages over traditional enzymes, such as enhanced stability, tunable catalytic activity, and multifunctionality. However, despite the increasing number of studies in this field, critical challenges remain, including the long‐term stability, the lack of studies on structure–activity relationships to better understand the catalytic mechanisms, and the scalability required for real‐world applications. This mini‐review provides a comprehensive overview of the most recent advancements in MXenzymes, focusing on the type of MXenes used, the reported enzyme‐like activity, and the role of the photothermal effects in enhancing their catalytic performance. Moreover, key limitations, such as oxidation susceptibility, biocompatibility concerns, and the scarce in‐depth mechanistic studies, are critically examined. Last, the necessary steps to transition from proof‐of‐concept studies to real‐world applications are discussed. By addressing the listed fundamental challenges, MXenzymes could represent a valuable and effective alternative to natural enzymes used in catalysis, medicine, and environmental science.more » « less
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            Abstract Surface chemistry and core composition of 2D MXenes play a major role in their interfacial properties, but the determination and quantification of their bonding environments remain challenging. X‐ray Photoelectron Spectroscopy (XPS) is a method of choice that is broadly utilized but is often hindered by large uncertainties and systematic bias due to adsorbed species such as adventitious carbon or etching residues. In this work, energy‐dependent XPS and depth profile modeling of the Ti3C2TxMXene surface are employed to differentiate the contributions from the MXene and the adsorbed species, thereby increasing the accuracy of quantification. In comparison, uncorrected lab‐based XPS suffers from a systematic overestimation of Ti vacancies by 7% and an underestimation of terminal atoms, particularly F, by as much as 15%. Interestingly, it is found that a simple inelastic mean free path correction is sufficient to address the issue and reveals extremely low defects in Ti3C2TxMXene synthesized using the HF/HCl etching route. Soft X‐ray Absorption Spectroscopy (XAS), supported by Density Functional Theory (DFT) calculations, also demonstrates a high chemical sensitivity of the surface terminations. This work provides novel insights into XPS quantification and the use of XAS for probing the carbide core and surface chemistry of Ti3C2TxMXenes.more » « less
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            Abstract Inorganic–organic hybrid MXenes (h‐MXenes) are a family of 2D transition metal carbides and nitrides functionalized with alkylimido and alkylamido surface groups. Using cryogenic and room temperature scanning transmission electron microscopy (STEM) and electron energy‐loss spectroscopy (EELS), it is shown that ripplocations, a form of a fundamental defect in 2D and layered structures, are abundant in this family of materials. Furthermore, detailed studies of electron probe sample interactions, focusing on structural deformations caused by the electron beam are presented. The findings indicate that at cryogenic temperatures (≈100 K) and below a specific dose threshold, the structure of h‐MXenes remains largely intact. However, exceeding this threshold leads to electron beam‐induced deformation through ripplocations. Interestingly, the deformation behavior, required dose, and resultant structure are highly dependent on temperature. At 100 K, it is demonstrated that the electron beam can induce ripplocations in situ with a high degree of precision.more » « less
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            Abstract Due to the ubiquity of textiles in the lives, electronic textiles (E‐textiles) have emerged as a future technology capable of addressing a myriad of challenges from mixed reality interfaces, on‐garment climate control, patient diagnostics, and interactive athletic wear. However, providing sufficient electrical power in a textile form factor has remained elusive. To address this issue, different approaches are discussed, starting with supercapacitors' advantages and limitations and material choices for textile‐based supercapacitors before discussing proper data analysis and design considerations of textile‐based energy storage to power wearable electronics.more » « less
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            Abstract Polyvinylidene fluoride (PVDF) is a semicrystalline polymer used in thin‐film dielectric capacitors because of its inherently high dielectric constant and low loss tangent. Its dielectric constant can be increased by the formation and alignment of its β‐phase crystalline structure, which can be facilitated by 2D nanofillers. 2D carbides and nitrides, MXenes, are promising candidates due to their notable dielectric permittivity and ability to increase interfacial polarization. Still, their mixing is challenging due to weak interfacial interactions and poor dispersibility of MXenes in PVDF. This work explores a novel method for delaminating Ti3C2TxMXene directly into organic solvents while maintaining flake size and quality, as well as the use of a non‐solvent‐induced phase separation method for producing both dense and porous PVDF‐MXene composite films. A deeper understanding of dielectric behavior in these composites is reached by examining MXenes with both mixed and pure chlorine terminations in PVDF matrices. Thin‐film capacitors fabricated from these composites display ultrahigh discharge energy density, exceeding 45 J cm−3with 95% efficiency. The PVDF‐MXene composites are also processed using a green and sustainable solvent, propylene carbonate.more » « less
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            Evolution of Surface Chemistry in Two‐Dimensional MXenes: From Mixed to Tunable Uniform TerminationsAbstract 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.more » « less
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            Abstract Achieving both high redox activity and rapid ion transport is a critical and pervasive challenge in electrochemical energy storage applications. This challenge is significantly magnified when using large‐sized charge carriers, such as the sustainable ammonium ion (NH4+). A self‐assembled MXene/n‐type conjugated polyelectrolyte (CPE) superlattice‐like heterostructure that enables redox‐active, fast, and reversible ammonium storage is reported. The superlattice‐like structure persists as the CPE:MXene ratio increases, accompanied by a linear increase in the interlayer spacing of MXene flakes and a greater overlap of CPEs. Concurrently, the redox activity per unit of CPE unexpectedly intensifies, a phenomenon that can be explained by the enhanced de‐solvation of ammonium due to the increased volume of 3 Å‐sized pores, as indicated by molecular dynamic simulations. At the maximum CPE mass loading (MXene:CPE ratio = 2:1), the heterostructure demonstrates the strongest polymeric redox activity with a high ammonium storage capacity of 126.1 C g−1and a superior rate capability at 10 A g−1. This work unveils an effective strategy for designing tunable superlattice‐like heterostructures to enhance redox activity and achieve rapid charge transfer for ions beyond lithium.more » « less
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            Abstract MXenes are promising passive components that enable lithium‐sulfur batteries (LSBs) by effectively trapping lithium polysulfides (LiPSs) and facilitating surface‐mediated redox reactions. Despite numerous studies highlighting the potential of MXenes in LSBs, there are no systematic studies of MXenes’ composition influence on polysulfide adsorption, which is foundational to their applications in LSB. Here, a comprehensive investigation of LiPS adsorption on seven MXenes with varying chemistries (Ti2CTx, Ti3C2Tx, Ti3CNTx, Mo2TiC2Tx, V2CTx, Nb2CTx, and Nb4C3Tx), utilizing optical and analytical spectroscopic methods is performed. This work reports on the influence of polysulfide concentration, interaction time, and MXenes’ chemistry (transition metal layer, carbide and carbonitride inner layer, surface terminations and structure) on the amount of adsorbed LiPSs and the adsorption mechanism. These findings reveal the formation of insoluble thiosulfate and polythionate complex species on the surfaces of all tested MXenes. Furthermore, the selective adsorption of lithium and sulfur, and the extent of conversion of the adsorbed species on MXenes varied based on their chemistry. For instance, Ti2CTxexhibits a strong tendency to adsorb lithium ions, while Mo2TiC2Txis effective in trapping sulfur by forming long‐chain polythionates. The latter demonstrates a significant conversion of intermediate polysulfides into low‐order species. This study offers valuable guidance for the informed selection of MXenes in various functional components benefiting the future development of high‐performance LSBs.more » « less
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            Free, publicly-accessible full text available September 1, 2026
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