An official website of the United States government
Abstract Ti3C2Tx(MXenes) are novel 2D nanomaterials with exceptional electrical conductivity. Their surfaces are covered with functional groups that may significantly affect material properties such as hydrophobicity, electrical conductivity, and oxidation resistance. The role of these terminations in high-temperature ceramic systems with regard to phase and microstructural evolution has not been investigated. In this study, Ti3C2Tx-SiOC 2D nanocomposites were fabricated with -F and -OH terminated MXene to evaluate the role of surface terminations in silane coupling and phase formation during the polymer-to-ceramic transformation. X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) identified self-etching mechanisms caused by F-terminated Ti3C2Txand revealed that the F surface terminations were retained in the MXene structure until evolution at ~ 550 °C. Evolved F reacted with Si–H bonds in the transforming ceramic matrix, causing additional mass loss and volumetric deformation. LiOH alkalization was shown to suppress the self-etching phenomenon through the substitution of F groups with OH on the nanosheet surface. Furthermore, F terminations were determined to only engage in hydrogen bonding with silane molecules as opposed to covalent linkages with OH terminations, which accelerated silane removal and Ti3C2Txdegradation. The study provides a fundamental understanding of the nature and behavior of MXene surface terminations in the context of high-temperature ceramic nanocomposite fabrication.
more »
« less
Evolution of Surface Chemistry in Two‐Dimensional MXenes: From Mixed to Tunable Uniform Terminations
Abstract 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
- PAR ID:
- 10531607
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 63
- Issue:
- 37
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Versatile chemical transformations of surface functional groups in two-dimensional transition-metal carbides (MXenes) open up a previously unexplored design space for this broad class of functional materials. We introduce a general strategy to install and remove surface groups by performing substitution and elimination reactions in molten inorganic salts. Successful synthesis of MXenes with oxygen, imido, sulfur, chlorine, selenium, bromine, and tellurium surface terminations, as well as bare MXenes (no surface termination), was demonstrated. These MXenes show distinctive structural and electronic properties. For example, the surface groups control interatomic distances in the MXene lattice, and Tin+1Cn(n= 1, 2) MXenes terminated with telluride (Te2−) ligands show a giant (>18%) in-plane lattice expansion compared with the unstrained titanium carbide lattice. The surface groups also control superconductivity of niobium carbide MXenes.more » « less
-
Abstract MXenes are a rapidly growing family of 2D transition metal carbides and nitrides that are promising for various applications, including energy storage and conversion, electronics, and healthcare. Hydrofluoric‐acid‐based etchants are typically used for large‐scale and high‐throughput synthesis of MXenes, which also leads to a mixture of surface terminations that impede MXene properties. Herein, a computational thermodynamic model with experimental validation is presented to explore the feasibility of fluorine‐free synthesis of MXenes with uniform surface terminations by dry selective extraction (DSE) from precursor MAX phases using iodine vapors. A range of MXenes and respective precursor compositions are systematically screened using first‐principles calculations to find candidates with high phase stability and low etching energy. A thermodynamic model based on the “CALculation of PHAse Diagrams” (CALPHAD) approach is further demonstrated, using Ti3C2I2as an example, to assess the Gibbs free energy of the DSE reaction and the state of the byproducts as a function of temperature and pressure. Based on the assessment, the optimal synthesis temperature and vapor pressure are predicted and further verified by experiments. This work opens an avenue for scalable, fluorine‐free dry synthesis of MXenes with compositions and surface chemistries that are not accessible using wet chemical etching.more » « less
-
null (Ed.)Two-dimensional materials based on transition metal carbides have been intensively studied due to their unique properties including metallic conductivity, hydrophilicity and structural diversity and have shown a great potential in several applications, for example, energy storage, sensing and optoelectronics. While MXenes based on magnetic transition elements show interesting magnetic properties, not much is known about the magnetic properties of titanium-based MXenes. Here, we measured the magnetic properties of Ti3C2Tx MXenes synthesized by different chemical etching conditions such as etching temperature and time. Our magnetic measurements were performed in a superconducting quantum interference device (SQUID) vibrating sample. These data suggest that there is a paramagnetic-antiferromagnetic (PM-AFM) phase transition and the transition temperature depends on the synthesis procedure of MXenes. Our observation indicates that the magnetic properties of these MXenes can be tuned by the extent of chemical etching, which can be beneficial for the design of MXenes-based spintronic devices.more » « less
-
Abstract Water pollution is a major global challenge, as conventional polymeric membranes are not adequate for water treatment anymore. Among emerging materials for water treatment, composite membranes are promising, as they have simultaneously improved water permeation and ions rejection. Recently, a new family of 2D materials called MXenes has attracted considerable attention due to their appealing properties and wide applications. MXenes can be incorporated into many polymeric materials due to their high compatibility. MXenes/polymer composite membranes have been found to have appealing electrical, thermal, mechanical, and transport properties, because of strong interactions between polymer chains and surface functional groups of MXenes and the selective nanochannels that are created. This article reviews advances made in the area of ion‐selective MXene‐based membranes for water purification. It puts the advances into perspective and provides prospects. MXenes’ properties and synthesis methods are briefly described. Strategies for the preparation of MXene‐based membranes including mixed‐matrix membranes, thin‐film nanocomposite membranes, and laminated membranes are reviewed. Recent advances in ion‐separation and water‐desalination MXene‐based membranes are elucidated. The dependence of ion‐separation performance of the membranes on fabrication techniques, MXene's interlayer spacing, and MXene's various surface terminations are elucidated. Finally, opportunities and challenges in ion‐selective MXene‐based membranes are discussed.more » « less
