Mxenes as 2D Inorganic Materials Layered

Structure, Modification and Characterization

Introduction:
In recent years, there has been a growing interest in two-dimensional materials due to their
unique electronic, mechanical, and thermal properties, which differ significantly from those of
their bulk counterparts. Graphene, in particular, has been the subject of intense research due to its
exceptional properties such as high electrical conductivity, optical transparency, mechanical
strength, and thermal conductivity. Graphene is a two-dimensional material composed of carbon
atoms arranged in a honeycomb lattice.
Following the discovery of graphene, scientists began to explore other two-dimensional
materials, such as silicene, phosphorene, h-BN, and MoS2. These materials have attracted
significant interest due to their potential applications in fields such as electronics,
optoelectronics, and energy storage.
In 2011, researchers from Drexel University discovered a new class of two-dimensional
materials known as MXenes. MXenes are composed of transition metals, carbon or nitrogen, and
elements from groups IIIA or IVA. They are synthesized by selectively etching the A element
from the MAX phases, which are materials with a hexagonal structure. This process leads to the
formation of MXene layers with an "accordion-like" structure, where the metal atoms are
connected through strong metallic bonds, while the layers are held together through weaker van
der Waals interactions.
MXenes exhibit several unique properties that make them attractive for various applications. For
example, they have a large specific surface area, which makes them useful for energy storage
and catalysis. MXenes also exhibit high mechanical strength, which makes them suitable for use
in flexible electronics and composites. Additionally, MXenes have excellent biocompatibility,
which makes them potential candidates for biomedical applications.
MXenes can be further modified through surface functionalization, which involves attaching
functional groups to the surface of the material. Surface functionalization can be achieved
through chemical reactions with various substances such as hydrofluoric acid (HF), which can
lead to the formation of F- and O/OH-terminated surfaces. This ability to control the surface
chemistry of MXenes opens up new avenues for the development of materials with tailored
properties for specific applications.
Overall, MXenes are a promising class of two-dimensional materials with a wide range of
potential applications. Their unique properties, coupled with the ability to modify their
physicochemical properties through surface functionalization, make them an exciting area of
research with significant potential for future technological advancements.
Background and motivation:
The field of 2D materials has undergone a significant transformation since the discovery of graphene in
2004. Researchers have been able to synthesize a range of 2D materials with unique properties and
potential applications. One such class of materials that has gained attention in recent years is MXenes.
MXenes are 2D Nano layers that consist of carbides, nitrides, or carbonitrides of transition metals. They
have been shown to exhibit exceptional properties, including excellent mechanical strength, thermal
conductivity, and electrical conductivity, making them attractive for various applications. Moreover,
MXenes have also shown promising results in the fields of energy storage, electrocatalysis, sensing, and
biomedical applications.

The excellent properties of MXenes, coupled with their unique structure, make them a promising
candidate for a wide range of applications. For example, their high specific surface area and excellent
biocompatibility make them suitable for use in biomedical applications. Additionally, their high electrical
conductivity and good catalytic properties make them suitable for energy storage and electrocatalytic
applications. As a result, there has been considerable interest in the synthesis, characterization, and
applications of MXenes. In this context, researchers are continually exploring new MXene structures and
applications to expand their potential use in various fields.

Objectives of the chapter:

The objective of studying MXenes as 2D inorganic materials with a layered structure is to gain a better
understanding of their properties and potential applications. By exploring the synthesis and
characterization of MXenes, researchers aim to identify and optimize their unique properties, such as
high specific surface area, good catalytic properties, and excellent biocompatibility. Additionally, the
objective is to explore the potential of MXenes for various applications, including energy storage,
electrocatalysis, sensing, and biomedical applications. Ultimately, the goal is to develop a deeper
understanding of MXenes and their potential applications to contribute to the development of new
materials with superior properties and performance.
Figure 1 (Graphical abstracts)

Overview of MXenes:
Definition and history of MXenes:
MXenes are a class of 2D materials that were first discovered in 2011 by
researchers at Drexel University. They are derived from MAX phases, which are ternary carbides
or nitrides with a layered structure. MXenes are produced by selectively etching the A element
from the MAX phase, leaving behind a 2D layer of transition metal carbide or nitride. The
resulting material has the general formula of M_n+1X_nT_x, where M is a transition metal, X is
carbon or nitrogen, T is a surface functional group, and n is usually 1, 2, or 3.

Method of synthesis of MXenes:

Here are some essay methods that has been used for the preparation of MXenes:

1) Selective etching method:

This is the most common method used for the synthesis of MXenes. This method involves the
removal A – layer (usually aluminum) from a max phase (usually Ti3AlC2) through etching
using hydrofluoric acid or mixture of hydrochloric and hydrofluoric acid. The steps involve in
these methods are given below,
 Synthesis of the MAX phase
 Etching of the A-layer
 Washing and delamination
  Drying and annealing
2) Intercalation method:
The intercalation method involves the insertion of guest molecules between the layer of the
precursor materials, involving the rules of Exfoliation to get MXenes. This method has been used
to prepare MXenes from the Graphite and Transition metal dichalcogenides. The stages of
synthesis involved in the method are as follows,
 Synthesis of the precursor materials
 Intercalation of the guest molecules
 Exfoliations
 Washing and drying
3) Sol-Gel method:
The sol-gel method is used to synthesize the precursor Sol which is then converted into a gel and
at last calcined to obtain the final product from the gel precursor. This method has been used to
prepare MXenes from the Alkoxide like titanium-alkoxides and other relative precursors. The
steps involve in this method are headed as follow,
 Synthesis of the precursor Sol
 Gelation
 Calcination
 Washing and drying
4) Electrochemical method:
The electrochemical method involves the electrochemical intercalation of the lithium ions into
MAX phase involving Exfoliation to obtain the desired product of MXenes. This method is
mostly used to prepare mxenes usually from (TI3AlC2) and other MAX phases. The steps used
in this method are as follows,
 Synthesis of the MAX phase
 Electrochemical intercalation of the lithium ions
 Exfoliations
 Washing and drying
5) Microwave assisted method:
This method used to rapidly heat up the precursor material by using microwaves to obtained the
final product of mxenes. This method has been used to prepare MXenes from the MAX phases
and other precursors. The steps involve in this method are given below,
o Synthesis of the precursor materials
o Microwaves irradiations
o Washing and drying
6) Chemical vapor deposition method:
The chemical vapor deposition method is used to synthesize mxenes through the deposition of
the gaseous precursor on the substrate molecules. This method has been used to prepared mxenes
from Titanium halides and other precursors. The main steps of this method are,
 Deposition of the precursor gas
 Formation of MXenes
 Washing and drying
These are some methods that has been used for the preparation of MXenes. Each method has its
own advantages and limitations and mostly the choice of the method depends upon on the
specific requirements of the application and the raw chemicals availability in the lab.

More chief and essay method:

The most commonly used method for the preparation of mxenes is the elective etching method.
This method is preferred because of a simple, low cost, and efficient method for the preparation
of MXenes.
This method also allows for the controlled synthesis of mxenes with specific properties, such as
thickness, conductivity and surface chemistry. Additionally, the selective etching method can be
used to prepare mxenes from a wide range of MAX phases, including TI3AlC2, Ti2AlC, V2AlC
and Nb2C etc.
Other methods, such as the intercalation method, sol-gel method, and electrochemical
method, have also been used for the preparation of MXenes. However, these methods are less
commonly used and have some limitations. The intercalation method is limited to the preparation
of MXenes from specific precursor materials, such as graphite and transition metal
dichalcogenides. The sol-gel method is a complex and time-consuming method, and it requires
specialized equipment and expertise. The electrochemical method is limited to the preparation of
MXenes from Ti3AlC2 and requires a high level of control to ensure the intercalation and
exfoliation processes are successful.
In summary, the selective etching method is the most commonly used and efficient method for
the preparation of MXenes, while other methods have some limitations and are less commonly
used.

Structure of MXene:
Crystal structure:
The layered crystal structure of MXenes has a similarity to that of graphene. The intercalated
functional groups separate the layers of transition metal carbides, nitrides, or carbonitrides.
The combination of face-centered cubic (FCC) and hexagonal close-packed (HCP) lattices can be
applied to characterise the crystal structure of MXenes. According to the demonstration, the
transition metal layers generate an HCP lattice, and the intercalated functional groups occupy
the FCC lattice's positions.