Solid-Solution MXenes: Synthesis, Properties, and Applications

ConspectusMXenes, among other two-dimensional (2D) materials such as graphene, hexagonal BN, transition metal dichalcogenides (TMDs), 2D metal-organic frameworks (MOFs), and covalent organic frameworks (COFs), are the fastest growing class discovered thus far. The general formula of MXenes is M_<i>n</i>+1X_<i>n</i>T_<i>x</i>, where M, X, and T_<i>x</i> represent an early transition metal (Ti, V, Nb, Mo, etc.), C and/or N, and the surface functional groups (typically, O, OH, F, Cl), respectively, and <i>n</i> can be between 1 and 4. MXenes as a class of materials have extraordinary properties, such as high electrical conductivity, nonlinear optical properties, solution processability, scalability and ease of synthesis, redox capability, and tunable surface properties, among others; the specific properties, however, depend on their chemistry. Since the initial report of the first MXene in 2011, the research community has primarily focused on Ti₃C₂T_<i>x</i>, and the amount of research work to investigate its synthesis and properties has increased exponentially over the years. In materials science, alloying is a useful way of synthesizing new materials to improve the properties of a class of materials. Advancement of steel and synthesis of inorganic semiconductors can be regarded as some of the major historical advancements in the concept of alloying. Thus, just one year after the initial report of MXenes, the first solid-solution MXene, (TiNb)₂CT_<i>x</i>, was reported, which demonstrates the inherent chemical tunability of this class of materials.MXenes have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites, presenting promising routes for tailoring their properties. X-site solid-solutions include carbonitride MXenes and are the least studied class of MXenes to date. Comparatively, multi-M MXenes have acquired significant attention, leading to the extreme example of high-entropy solid-solution MXenes. By using multiple M elements, a significant expansion of the structural and chemical diversity is possible, giving rise to novel chemical, magnetic, electronic, and optical properties that cannot be accessed by single-M MXenes. Solid-solution MXenes represent the largest and most tunable class of MXenes; solid-solution MXenes are those that have multiple metals that are randomly distributed on their M sites with no distinct chemical ordering. Using multiple M elements in MXenes, it is possible to synthesize novel MXene structures that cannot be produced otherwise, such as M₅X₄T_<i>x</i> MXenes. Based on their chemistry, it is possible to rationally control the electronic, optical, mechanical, and chemical properties in a way that no other class of MXenes can. In some cases, the resultant property is linearly related to the chemistry, such as the electrical conductivity, while in other cases the properties are nonlinear or emergent: optical properties, enabling these MXenes to fulfill roles that no other MXene, or 2D material, can.In this Account, we discuss the recent progress in the synthesis, properties, applications, and outlook of solid-solution MXenes. Importantly, we demonstrate how multi-M solid-solutions can be used to tailor properties for specific applications easily.