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Two-dimensional (2D) transition metal carbides, nitrides and carbonitrides, known as MXenes, are of interest as electrocatalysts. Tungsten-based MXenes are predicted to have low overpotentials in the hydrogen evolution reaction but their synthesis has proven difficult due to the calculated instability of their hypothetical MAX precursors. In this study, we present a theory-guided synthesis of a tungsten-based MXene, W2TiC2Tx, derived from a non-MAX nanolaminated ternary carbide (W,Ti)4C4−y precursor by the selective etching of one of the covalently bonded tungsten layers. Our results indicate the importance of tungsten and titanium ordering, the presence of vacancy defects in the metal layers, and the lack of oxygen impurities in the carbon layers for the successful selective etching of the precursor. We confirm the atomistic out-of-plane ordering of tungsten and titanium using computational and experimental characterizations. The tungsten-rich basal plane endows W2TiC2Tx MXene with a high electrocatalytic hydrogen evolution reaction performance (∼144 mV overpotential at 10 mA cm−2). This study reports a tungsten-based MXene synthesized from a covalently bonded non-MAX precursor, adding to the synthetic strategies for 2D materials. 

In compositionally complex materials, there is controversy on the effect of enthalpy versus entropy on the structure and short-range ordering in so-called high-entropy materials. To help address this controversy, we synthesized and probed 40 M4AlC3 layered carbide phases containing 2 to 9 metals and found that short-range ordering from enthalpy is present until the entropy increases enough to achieve complete disordering of the transition metals in their atomic planes. We transformed all these layered carbide phases into two-dimensional (2D) sheets and showed the effects of the order vs. disorder on their surface properties and electronic behavior. This study suggests the key effect that the competition between enthalpy and entropy has on short-range order in multi-compositional materials. 

Synovial joints, critical for limb biomechanics, rely on sophisticated lubrication systems to minimize wear. Disruptions, whether from injury or disease, often necessitate joint replacements. While additive manufacturing offers personalized implants, ensuring wear resistance remains a challenge. This study delves into the potential of Ti3C2Tx and Mo2TiC2Tx nanosheets in mitigating wear of additively manufactured cobalt-chromium tungsten alloy substrates when incorporated as additives into synovial fluid. The colloidal solutions demonstrate an excellent stability, a crucial factor for reproducible assays and potential clinical applicability. Analysis of contact angles and surface tensions reveals MXene-induced alterations in substrate wettability, while maintaining their general hydrophilic character. Viscosity analysis indicates that MXene addition reduces the dynamic viscosity, particularly at higher concentrations above 5 mg/mL, thus enhancing dispersion and lubrication properties. Friction and wear tests demonstrate a dependency on the MXene concentration, while Ti3C2Tx exhibits stable friction coefficients and up to 77 % wear reduction at 5 mg/mL, which was attributed to the formation of a wear-protecting tribo-film (amorphous carbon and MXene nano-sheets). Our findings suggest that Ti3C2Tx, when supplied in favorable concentrations, holds promise for reducing wear in biotribological applications, offering avenues for future research into optimizing MXene utilization in load-bearing joint replacements and other biomedical devices. 

Two-dimensional transition metal carbides, nitrides, and carbonitrides, known as MXenes, hold potential in electrocatalytic applications. Tungsten (W) based-MXenes are of particular interest as they are predicted to have low overpotentials in hydrogen evolution reaction (HER). However, incorporating W into the MXene structure has proven difficult due to the calculated instability of its hypothetical MAX precursors. In this study, we present a theory-guided synthesis of a W-containing MXene, W2TiC2Tx, derived from a non-MAX nanolaminated ternary carbide (W,Ti)4C4-y precursor by selective etching of one of the covalently bonded tungsten layers. Our results indicate the importance of W and Ti ordering and the presence of vacancy defects for the successful selective etching of the precursor. We confirm the atomistic out-of-plane ordering of W and Ti using density functional theory, Rietveld refinement, and electron microscopy methods. Additionally, the W-rich basal plane endows W2TiC2Tx MXene with a remarkable HER overpotential (~144 mV at 10 mA/cm2). This study adds a tungsten-containing MXene made from a covalently bonded non-MAX phase opening more ways to synthesize novel 2D materials. 

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