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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. 

Abstract The origin of MXene's excellent electromagnetic shielding performance is not fully understood. MXene films, despite being inhomogeneous at the nanometer scale, are often treated as if they are compared to bulk conductors. It is reasonable to wonder if the treatment of MXene as a homogeneous material remains valid at very small film thickness and if it depends on the interlayer spacing. The goal of the present work is to test if the homogeneous material model is applicable to nanometer‐thin Ti₃C₂T_xMXene films and, if so, to investigate how the model parameters may depend on variations in MXene interlayer spacings. MXene films containing flakes with interlayer spacing between 1.9 and 5.5 Å have been prepared using various intercalating agents. It is shown that modeling the films as being homogeneous agrees with experimental tests in the microwave frequency range. Microwave conductivity and dielectric constant parameters are estimated for the homogeneous film model by fitting measured results. The direct current (DC) conductivity matches the estimated microwave conductivity on the order of magnitude. A highly effective dielectric constant provides a good fit for the lower conductivity MXene films. Optical absorption agrees with the homogeneous material model of thin films as well. 

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 (Ti₂CT_x, Ti₃C₂T_x, Ti₃CNT_x, Mo₂TiC₂T_x, V₂CT_x, Nb₂CT_x, and Nb₄C₃T_x), 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, Ti₂CT_xexhibits a strong tendency to adsorb lithium ions, while Mo₂TiC₂T_xis 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.