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 (Ti3C2T
This content will become publicly available on April 18, 2025
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.
more » « less- Award ID(s):
- 2419026
- PAR ID:
- 10540254
- Publisher / Repository:
- ChemRvix
- Date Published:
- Format(s):
- Medium: X
- Institution:
- Purdue University
- Sponsoring Org:
- National Science Foundation
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Abstract x ) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric‐Ti3AlC2MAX phase and delamination of the etched multilayered Ti3C2Tx 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 Ti3AlC2, 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 Ti3C2Tx 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 Ti3C2Tx MXene synthesis as the supporting information for this study. -
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Abstract Since their discovery in 2011, the number of 2D transition metal carbides and nitrides (MXenes) has steadily increased. Currently more than 40 MXene compositions exist. The ultimate number is far greater and in time they may develop into the largest family of 2D materials known. MXenes’ unique properties, such as their metal‐like electrical conductivity reaching ≈20 000 S cm−1, render them quite useful in a large number of applications, including energy storage, optoelectronic, biomedical, communications, and environmental. The number of MXene papers and patents published has been growing quickly. The first MXene generation is synthesized using selective etching of metal layers from the MAX phases, layered transition metal carbides and carbonitrides using hydrofluoric acid. Since then, multiple synthesis approaches have been developed, including selective etching in a mixture of fluoride salts and various acids, non‐aqueous etchants, halogens, and molten salts, allowing for the synthesis of new MXenes with better control over their surface chemistries. Herein, a brief historical overview of the first 10 years of MXene research and a perspective on their synthesis and future development are provided. The fact that their production is readily scalable in aqueous environments, with high yields bodes well for their commercialization.
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Abstract 2D early transition metal carbide and nitride MXenes have intriguing properties for electrochemical energy storage and electrocatalysis. These properties can be manipulated by modifying the basal plane chemistry. Here, mixed transition metal nitride MXenes, M‐Ti4N3Tx(M = V, Cr, Mo, or Mn; Tx= O and/or OH), are developed by modifying pristine exfoliated Ti4N3TxMXene with V, Cr, Mo, and Mn salts using a simple solution‐based method. The resulting mixed transition metal nitride MXenes contain 6–51% metal loading (cf. Ti) that exhibit rich electrochemistry including highly tunable hydrogen evolution reaction (HER) electrocatalytic activity in a 0.5
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null (Ed.)Quaternary MAX phases, (Ta 1−x Ti x ) 3 AlC 2 ( x = 0.4, 0.62, 0.75, 0.91 or 0.95), have been synthesised via pressureless sintering of TaC, TiC, Ti and Al powders. Via chemical etching of the Al layers, (Ta 0.38 Ti 0.62 ) 3 C 2 T z – a new MXene, has also been synthesised. All materials contain an M-layer solid solution of Ta and Ti, with a variable Ta concentration, paving the way for the synthesis of a range of alloyed (Ta,Ti) 3 C 2 T z MXenes with tuneable compositions for a wide range of potential applications.more » « less
