Louisiane Verger

Chuan Xu

Varun Natu

Hui-Ming Cheng

Wencai Ren
email: wcren@imr.ac.cn

Michel W Barsoum
email: barsoumw@drexel.edu

Overview of the Synthesis of MXenes and Other Ultrathin 2D Transition Metal Carbides and Nitrides

Keywords: MXenes, 2D materials, top-down synthesis, bottom-up synthesis

In 2011, a new family of two dimensional (2D) carbides, carbonitrides and nitrides -labeled MXenes -was discovered. Since then the number of papers on these materials has increased exponentially for several reasons amongst them: their hydrophilic nature, excellent electronic conductivities and ease of synthesizing large quantity in water. This unique combination of properties and ease of processing has positioned them as enabling materials for a large and quite

varied host of applications from energy storage to electromagnetic shielding to transparent conductive electrodes, electrocatalysis, to name a few. Since the initial synthesis of Ti3C2 in hydrofluoric acid, many more compositions were discovered, and different synthesis pathways were explored. Most of the work done so far has been conducted on top-down synthesis where a layered parent compound is etched and then exfoliated. Three bottom-up synthesis methods, chemical vapor deposition, a template method and plasma enhanced pulsed laser deposition have been reported. The latter methods enable the synthesis of not only high-quality thin 2D transition metal carbide and nitride films, but also those that could not be synthesized by selective etching.

This article reviews and summarizes the most important breakthroughs in the synthesis of MXenes and high-quality thin 2D transition metal carbide and nitride films.

Highlights:

• Currently MXenes constitute a family of 2D materials of about 30 different compositions obtained by top-down synthetic methods. The vast majority of these compositions involve the etching of a MAX phase using a F-ion containing solution such as HF or LiF and HCl.

• Bottom-up synthesis enables the production of not only high-quality thin 2D transition metal carbide and nitride films but also those that could not be synthesized by selective etching.

• Different synthesis pathways have been reported that avoid the use of hazardous HF, mainly for the most studied compound Ti3C2.

• The possibility of solid solutions of the M and X sites, and chemical order in and out of plane in the MAX phases has greatly expanded the chemistry of MXenes.

Introduction

Over the last decade, two dimensional (2D) materials has garnered their fair share of research interest due to their exciting physical and chemical properties and extensive application potential [START_REF] Nicolosi | Liquid Exfoliation of Layered Materials[END_REF] . Since the first synthesis of graphene [START_REF] Novoselov | Electric field effect in atomically thin carbon films[END_REF] , the field has broadened to many other 2D materials, such as boron nitride [START_REF] Golberg | Boron Nitride Nanotubes and Nanosheets[END_REF] , metal dichalcogenides [START_REF] Wang | Electronics and optoelectronics of two-dimensional transition metal dichalcogenides[END_REF] , halides [START_REF] Coleman | A Review of Intercalation in Heavy Metal Iodides[END_REF] and oxides [START_REF] Ma | Nanosheets of Oxides and Hydroxides: Ultimate 2D Charge-Bearing Functional Crystallites[END_REF] among others.

One of the most recent addition to the 2D family of materials are transition metal carbides, carbonitrides and nitrides (MXenes) [START_REF] Naguib | Two-Dimensional Transition Metal Carbides[END_REF] . Their formula can be M1.33XTz or Mn+1XnTz (n = 1, 2 or 3), where M is an early transition metal, X is C and/or N and Tz represents various possible terminations (mainly hydroxyl, -OH, oxygen, -O and/or fluorine, -F). They were dubbed MXenes because the vast majority of them are obtained by etching the Al layers from the MAX phases and their 2D nature [START_REF] Naguib | Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2[END_REF] . The MAX phases in turn are layered hexagonal transition metal carbide and nitrides [START_REF] Barsoum | MAX Phases: Properties of Machinable Ternary Carbides and Nitrides -Michel W. Barsoum[END_REF] . As noted above, the first MXene, Ti3C2Tz was produced in 2011 by placing Ti3AlC2 powders in concentrated HF for a few hours at room temperature [START_REF] Naguib | Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2[END_REF] . A year later, the universality of etching Al from many other MAX phases gave birth to MXenes [START_REF] Naguib | Two-Dimensional Transition Metal Carbides[END_REF] . Soon thereafter, MXenes showed great promise in a host of applications such as electrochemical energy storage [START_REF] Naguib | MXene: A promising transition metal carbide anode for lithium-ion batteries[END_REF] , with notably high capacitances [START_REF] Lukatskaya | Cation intercalation and high volumetric capacitance of twodimensional titanium carbide[END_REF] , structural composites [START_REF] Ling | Flexible and conductive MXene films and nanocomposites with high capacitance[END_REF] , electromagnetic interference shielding [START_REF] Han | Ti3C2 MXenes with Modified Surface for High-Performance Electromagnetic Absorption and Shielding in the X-Band[END_REF][START_REF] Shahzad | Electromagnetic interference shielding with 2D transition metal carbides (MXenes)[END_REF] , water purification [START_REF] Peng | Unique Lead Adsorption Behavior of Activated Hydroxyl Group in Two-Dimensional Titanium Carbide[END_REF] , biosensors [START_REF] Liu | A novel nitrite biosensor based on the direct electrochemistry of hemoglobin immobilized on MXene-Ti3C2[END_REF] , transparent conductive electrodes, among many more [START_REF] Anasori | 2D metal carbides and nitrides (MXenes) for energy storage[END_REF] .

In general, there are two methods to synthesize 2D materials. The first is a bottom-up approach, such as chemical vapor deposition (CVD) that can produce high-quality films on various substrates. This approach is not generally used to make MXenes, because the films obtained are not single layer, but rather very thin films. For example, Xu et al. [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF] used chemical vapor deposition (CVD) to produce thin Mo2C, WC and TaC films. However, even the thinnest Mo2C films were comprised of at least six Mo2C layers and not single MXenes sheets. This comment notwithstanding, it is one that should be pursued since in other systems it has been shown to yield high quality films [START_REF] Reina | Large Area, Few-Layer Graphene Films on Arbitrary Substrates by Chemical Vapor Deposition[END_REF][START_REF] Wang | Controlled Synthesis of Highly Crystalline MoS 2 Flakes by Chemical Vapor Deposition[END_REF] . This approach is discussed in some detail in part 2.

The second approach, is a top-down approach, involving the exfoliation of layered solids. This approach can be further divided into mechanical and chemical exfoliation. An example of the former is the use of adhesive tape to separate the graphene layers [START_REF] Novoselov | Electric field effect in atomically thin carbon films[END_REF] . This approach is unsuitable for the MAX phases for the simple reason that -in contrast to most other 3D solids used as precursors to their 2D counterparts -the bonds between the M elements and Al are for, the most part, strong covalent/metallic. Many Al-based MAX phases are synthesized at temperatures higher than 1300 °C [START_REF] Barsoum | MAX Phases: Properties of Machinable Ternary Carbides and Nitrides -Michel W. Barsoum[END_REF] . Since this approach is inapplicable here it will not be discussed further. It is worth noting that prior to the MXene discovery, conventional wisdom had it that only weakly bonded 3D solids can be exfoliated. In that sense, the MXene discovery was paradigm shifting.

The key to converting weakly bonded 3D solids to their 2D counterparts using the topdown approach is to weaken the interlayer bonds. One approach is to intercalate the layers to the point that they can be readily dispersed in a solvent. The main challenge thus lies in finding the right combination of intercalant and solvent [START_REF] Nicolosi | Liquid Exfoliation of Layered Materials[END_REF] . This approachmost usually carried out in liquids -is by far the preferred one when large quantities of material are needed. Four main types of liquid exfoliation methods are usually described in the literature. The first consists in treating the 3D layered solid with an oxidizer and the resulting material is then dispersed in the appropriate solvent. Graphene oxide (GO) is synthesized by this method, using sulfuric acid and permanganate potassium as the oxidizers and water as the solvent [START_REF] Dreyer | The chemistry of graphene oxide[END_REF] . A second method relies on the fact that the 3D layered solid can host various ionic species and/or guest molecules between the layers. Once that is accomplished the concomitant swelling can sufficiently weaken the interlayer attraction and lead to a 2D dispersion. Additional energetic treatment (shear, agitation, sonication) is sometimes needed to separate the 2D layers. For example, MoS2 can be dispersed by this method [START_REF] Joensen | Single-layer MoS2[END_REF] . Some layered materials already contain cationic counter ions that compensate their surface layer charges. For these solids, a third method entailing exchanging the intrinsic cations with, typically, larger ions, can result in the separation of the nanosheet under vigorous stirring. Vermiculite [START_REF] Walker | Chemical exfoliation of vermiculite and the production of colloidal dispersions[END_REF] or birnessite-type layered manganese oxides [START_REF] Liu | Swelling and delamination behaviors of birnessite-type manganese oxide by intercalation of tetraalkylammonium ions[END_REF] can be exfoliated using this method. The last, and most recent method, consists in directly exposing the 3D layered material to ultrasonic waves in a solvent that prevents their re-aggregation. This method was used on graphite using N-methylpyrrolidone (NMP) as a solvent for instance [START_REF] Hernandez | High-yield production of graphene by liquid-phase exfoliation of graphite[END_REF] . Since as noted above, MXenes are mostly derived from the MAX phases, in which the M-A layers are quite strongly bound to each other by a combination of covalent and metallic bonds [START_REF] Barsoum | MAX Phases: Properties of Machinable Ternary Carbides and Nitrides -Michel W. Barsoum[END_REF] neither mechanical nor classical chemical exfoliation is possible. What is required in this case is to first selectively etch the A layers (Figure 1). The purpose of this work is to give a brief overview of the different MXenes synthesized so far and some of their characteristics, with a focus on the different synthetic pathways used to obtain them. We will first describe top-down synthesis and some of the characteristics of the MXenes obtained, before focusing on the bottom-up approaches. This article complements existing review on MXenes, focused on energy storage [START_REF] Anasori | 2D metal carbides and nitrides (MXenes) for energy storage[END_REF][START_REF] Pang | Applications of 2D MXenes in energy conversion and storage systems[END_REF][START_REF] Xiao | Transition metal carbide-based materials: synthesis and applications in electrochemical energy storage[END_REF] , thin film production [START_REF] Eklund | Layered ternary Mn +1AX n phases and their 2D derivative MXene: an overview from a thin-film perspective[END_REF] , electrical and optical properties [START_REF] Hantanasirisakul | Electronic and Optical Properties of 2D Transition Metal Carbides and Nitrides (MXenes)[END_REF] , or composites [START_REF] Ng | Recent progress in layered transition metal carbides and/or nitrides (MXenes) and their composites: synthesis and applications[END_REF] .

Synthesis of MXenes by top-down approaches

Since the original discovery in 2011 of the first MXene, Ti3C2Tz, this family of 2D materials has expanded quite fast and today about 30 different compositions have been synthesized with more being discovered on a routine basis. Figure 2 and Figure 3 summarize the different MXenes obtained to date, their precursors, etching methods and highlights.

Precursors

The MAX phases constitute a large family of currently > 130 different compositions, the vast majority of which crystallize in the P63/mmc space group [START_REF] Barsoum | MAX Phases: Properties of Machinable Ternary Carbides and Nitrides -Michel W. Barsoum[END_REF] or derivatives thereof. The structure is composed of MX6 octahedra, interleaved with pure A layers. The main difference between the three types of MAX phases, viz. n = 1, 2 or 3, is in the number of M layers (2 to 4) between the A layers. They are typically referred to as 211, 312 or 413, respectively.

Of the ~ 30 different MXenes currently known, all but a handful are obtained by etching the Al layers from Al-containing MAX phases. There are a few exceptions. For example, Si etching of Ti3SiC2 yields Ti3C2Tz [START_REF] Alhabeb | Selective Etching of Silicon from Ti3SiC2 (MAX) To Obtain 2D Titanium Carbide (MXene)[END_REF] . The starting material to synthesize Mo2CTz is Mo2Ga2C [START_REF] Meshkian | Synthesis of two-dimensional molybdenum carbide, Mo2C, from the gallium based atomic laminate Mo2Ga2[END_REF][START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF] . And while technically speaking Mo2Ga2C is not a MAX phase, its structure is quite similar to the 211 structure, except that the MoC6 octahedra are interleaved by two Ga layers instead of one. More recently, another class of layered solids was used as precursors, viz. (MC)nAl3C2 and (MC)n(Al,Si)4C3, where Al3C3 and (Al,Si)4C4 were etched to yield Zr3C2Tz and Hf3C2Tz, respectively [START_REF] Zhou | A Two-Dimensional Zirconium Carbide by Selective Etching of Al3C3 from Nanolaminated Zr3Al3C5[END_REF][START_REF] Zhou | Synthesis and Electrochemical Properties of Two-Dimensional Hafnium Carbide[END_REF] .

The chemical or structural order in MXenes is directly linked to the order in the parent phase. Roughly a third (~ 50) of the known MAX phases to date were discovered by Nowotny and coworkers in the sixties [START_REF] Nowotny | Strukturchemie einiger Verbindungen der Übergangsmetalle mit den elementen C, Si, Ge[END_REF] . Up to the end of 2014, the only MAX phase solid solutions known on the M sites were random solid solutions [START_REF] Nowotny | Structural chemistry of complex carbides and related compounds[END_REF][START_REF] Naguib | New Solid Solution MAX Phases: (Ti0.5,V0.5)3AlC2[END_REF] , such as the 211 phases (TixNb1-x)2AlC [START_REF] Nowotny | Structural chemistry of complex carbides and related compounds[END_REF] and (TixCr1-x)2AlC [START_REF] Schuster | The ternary systems: CrAlC, VAlC, and TiAlC and the behavior of H-phases (M2AlC)[END_REF] , the 312 phase (Ti1/2V1/2)3AlC2, and the 413 phase (Cr5/8Ti3/8)4AlC3 [START_REF] Liu | Cr2/3Ti1/3)3AlC2 and (Cr5/8Ti3/8)4AlC3 : New MAX-phase Compounds in Ti-Cr-Al-C System[END_REF] , etc.

In 2014 and 2017, respectively, two new chemically ordered quaternary MAX phases were discovered: (i) out-of-plane ordered, labeled o-MAX, 312 and 413 phases and more recently, (ii) in-plane ordered, labeled i-MAX, 211 phases. In the former, a single layer or double layer of one metal element is sandwiched between a layer of another M element (see Figure 3) [START_REF] Liu | Cr2/3Ti1/3)3AlC2 and (Cr5/8Ti3/8)4AlC3 : New MAX-phase Compounds in Ti-Cr-Al-C System[END_REF][START_REF] Anasori | Mo2TiAlC2: A new ordered layered ternary carbide[END_REF] . Examples include (Cr2/3Ti1/3)3AlC2, (Mo2/3Ti1/3)3AlC2, (Mo1/2Ti1/2)4AlC3 and (Mo2/3Sc1/3)3AlC2, where the Ti or Sc layers are located in the inner layers and the Mo on the outside [START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF][START_REF] Meshkian | Theoretical stability and materials synthesis of a chemically ordered MAX phase, Mo2ScAlC2, and its two-dimensional derivate Mo2ScC2 MXene[END_REF] . In the i-MAX, the two M elements are in plane ordered (Figure 2). The quaternary (Mo2/3Sc1/3)2AlC is such a phase [START_REF] Tao | Two-dimensional Mo1.33C MXene with divacancy ordering prepared from parent 3D laminate with in-plane chemical ordering[END_REF] . The space group used to describe this structure is C2/c. The quaternaries, (Mo/3Y1/3)2AlC and (V2/3Zr1/3)3AlC2 were also just discovered [START_REF] Dahlqvist | Prediction and synthesis of a family of atomic laminate phases with Kagomé-like and in-plane chemical ordering[END_REF] , followed by two W-based phases, viz. (W2/3Sc1/3)2AlC and (W2/3Y1/3)2AlC [START_REF] Meshkian | W-Based Atomic Laminates and Their 2D Derivative W1.33C MXene with Vacancy Ordering[END_REF] . Most recently 11 Mo-based rare earth containing i-MAX phases were also discovered [START_REF] Tao | Atomically Layered and Ordered Rare-Earth i-MAX Phases: A New Class of Magnetic Quaternary Compounds[END_REF] .

Etching

In the MAX to MXene transformation, the etched layers are always replaced by various termination groups Tz such as hydroxyl (-OH), oxygen (-O) or fluorine (-F). The material obtained after etching thus consists of Mn+1XnTz multilayers (see Figure 1B) held together by hydrogen and/or van der Waals bonds. The different etching methods are described in this section.

The ternary, Ti3AlC2, is not only the first MAX to be etched [START_REF] Naguib | Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2[END_REF] , but also remains, by far, the most studied, and a variety of etching methods have been developed to convert it to Ti3C2Tz (see Figure 3). The first synthesis 8 consisted of immersing Ti3AlC2 powders in 50 wt.% hydrofluoric acid (HF). The M-A bonds and the M-X bonds reacted differently toward HF, resulting in the selective etching of the Al layers. HF etching was then successfully applied to obtain a wide variety of MXenes [START_REF] Naguib | Two-Dimensional Transition Metal Carbides[END_REF][START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF][START_REF] Ghidiu | Synthesis and characterization of two-dimensional Nb4C3 (MXene)[END_REF][START_REF] Yang | Two-Dimensional Nb-Based M4C3 Solid Solutions (MXenes)[END_REF][START_REF] Soundiraraju | Two-Dimensional Titanium Nitride (Ti2N) MXene: Synthesis, Characterization, and Potential Application as Surface-Enhanced Raman Scattering Substrate[END_REF][START_REF] Zhou | A Two-Dimensional Zirconium Carbide by Selective Etching of Al3C3 from Nanolaminated Zr3Al3C5[END_REF][START_REF] Zhou | Synthesis and Electrochemical Properties of Two-Dimensional Hafnium Carbide[END_REF][START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF][START_REF] Tao | Two-dimensional Mo1.33C MXene with divacancy ordering prepared from parent 3D laminate with in-plane chemical ordering[END_REF][START_REF] Naguib | New Two-Dimensional Niobium and Vanadium Carbides as Promising Materials for Li-Ion Batteries[END_REF][START_REF] Persson | Tailoring Structure, Composition, and Energy Storage Properties of MXenes from Selective Etching of In-Plane, Chemically Ordered MAX Phases[END_REF][START_REF] Naguib | A New Family of Two-Dimensional Materials and its Application as Electrodes for Li-ion Batteries[END_REF][START_REF] Tran | Adding a New Member to the MXene Family: Synthesis, Structure, and Electrocatalytic Activity for the Hydrogen Evolution Reaction of V4C3T x[END_REF] (see Figure 2 and Figure 3) and remains the most common synthetic pathway. The etching conditions, however, depend on the chemistry and structure of the parent phase. For example, 50 wt.% HF, used on Ti2AlC, results in its total dissolution. The same is true for Cr2AlC. However, by decreasing the HF concentration down to 10 wt.%, Ti2CTz can be obtained [START_REF] Naguib | Two-Dimensional Transition Metal Carbides[END_REF] , but this remains unsuccessful on Cr2AlC. Modifying the HF concentration during etching of the (Mo2/3Y1/3)2AlC i-MAX phase enables the selective etching of either only the Al (10 wt.% HF) layers or, both the Al and Y (50 wt.% HF) layers [START_REF] Persson | Tailoring Structure, Composition, and Energy Storage Properties of MXenes from Selective Etching of In-Plane, Chemically Ordered MAX Phases[END_REF] .

HF is a corrosive chemical, able to penetrate through skin, muscle tissue and bones, making its handling and disposal hazardous [START_REF] Lakhe | Process Safety Analysis for Ti3C2Tx MXene Synthesis and Processing[END_REF] . Different synthesis pathways have been explored to avoid or minimize the use of concentrated HF. One of the most widely used is a mixture of hydrochloric acid (HCl) and a fluoride salt, that forms HF in-situ. Ghidiu et al. first introduced this method using lithium fluoride (LiF) and HCl on Ti3AlC2 [START_REF] Ghidiu | Conductive two-dimensional titanium carbide 'clay' with high volumetric capacitance[END_REF] , and highlighted the analogy of MXenes with clays. Other fluoride salts have also been successfully used (NaF, KF and NH4F [START_REF] Liu | Preparation of Ti3C2 and Ti2C MXenes by fluoride salts etching and methane adsorptive properties[END_REF][START_REF] Liu | Preparation of High-Purity V2C MXene and Electrochemical Properties as Li-Ion Batteries[END_REF] ), as well as different HCl concentrations and LiF/HCl molar ratios [START_REF] Alhabeb | Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti3C2Tx MXene)[END_REF] . Ammonium hydrogen bifluoride (NH4HF2) was also used early on as an alternative to HF to etch Al from Ti3AlC2. It was firstly implemented on thin epitaxial Ti3AlC2 films [START_REF] Halim | Transparent Conductive Two-Dimensional Titanium Carbide Epitaxial Thin Films[END_REF] , and then used on powders [START_REF] Karlsson | Atomically Resolved Structural and Chemical Investigation of Single MXene Sheets[END_REF] .

Electrochemical etching in dilute HCl was carried out on Ti2AlC to yield Ti2CTz multilayers, but with the presence of carbide-derived carbon [START_REF] Sun | Electrochemical etching of Ti2AlC to Ti2CTx (MXene) in low-concentration hydrochloric acid solution[END_REF] . Another F-free etching method based on the anodic corrosion of Ti3AlC2 in an electrolyte mixture of NH4Cl and tetramethylammonium hydroxide (TMAOH) has been reported with a yield of > 40% [START_REF] Yang | Fluoride-Free Synthesis of Two-Dimensional Titanium Carbide (MXene) Using A Binary Aqueous System[END_REF] . Two new articles have been made available online through archive [START_REF] Lu | Tin+1Cn MXene with fully saturated and thermally stable Cl terminations[END_REF][START_REF] Li | An Element Replacement Approach by Reaction with Lewis acidic Molten Salts to Synthesize Nanolaminated MAX Phases and MXenes[END_REF] , where the authors describe the synthesis of fully Cl-terminated Ti3C2Tz and Ti2CTz MXenes from the reaction of Ti3AlC2 and Ti2AlC, respectively, in a Lewis acidic melt, such as ZnCl2.

Until recently, Al was the only element etched from the A layers of the MAX phases.

Alhabeb et al. showed for the first time the selective etching of Si from the MAX phase Ti3SiC2

31 . A mixture of HF and an oxidant (such as hydrogen peroxide, H2O2) was used. This new approach widens the type of MAX precursors possible, but the method needs to be optimized to increase the yields and quality of the 2D flakes obtained.

The HF and HCl/LiF etching methods are typically performed at temperatures < 60 °C. It is also possible to obtain MXenes at higher temperatures. An alkali-assisted hydrothermal method (using 27.5 M NaOH at 270 °C) was used to produce Ti3C2Tz. The first nitride MXene -Ti4N3Tzwas synthesized by heating Ti4AlN3 powders in a molten salt eutectic mixture of LiF, sodium fluoride (NaF), and potassium fluoride (KF) at 550 °C, under argon (Ar) [START_REF] Urbankowski | Synthesis of two-dimensional titanium nitride Ti4N3 (MXene)[END_REF] . More recently, V2NTz and Mo2NTz were obtained by the ammoniation of the carbides V2CTz and Mo2CTz at 600 °C [START_REF] Urbankowski | 2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes)[END_REF] . Precursors, etching method used to obtain them, and highlights are shown.

Exfoliation

After etching, the resulting multilayers (Figure 1 B) are typically washed several times with water to remove the etching solution containing the byproducts of the synthesis, such as aluminum fluoride (AlF3) [START_REF] Naguib | Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2[END_REF] . An acid-prewash with HCl, or sulfuric acid (H2SO4), can also be used to help dissolve salts such as AlF3 or LiF [START_REF] Urbankowski | Synthesis of two-dimensional titanium nitride Ti4N3 (MXene)[END_REF][START_REF] Ghidiu | Ion-Exchange and Cation Solvation Reactions in Ti3C2 MXene[END_REF] . It is only then that it is possible to exfoliate the multilayers and obtain colloidal suspensions comprised of single or a few MXene layers (Figure 1 C). The exfoliation techniques used depend on, (i) etching method and, (ii) MXene composition.

When multilayers are obtained by etchants other than HCl/LiF, direct sonication can be used to exfoliate them but the yields are quite low [START_REF] Naguib | Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2[END_REF] . Liquid exfoliation by the intercalation of molecules is then the main method used to obtain colloids with high yield (up to 20 mg of MXenes per mL of solution). Similar to clays, the multilayers can host various cations and organic molecules [START_REF] Ghidiu | Ion-Exchange and Cation Solvation Reactions in Ti3C2 MXene[END_REF][START_REF] Ghidiu | Alkylammonium Cation Intercalation into Ti3C2 (MXene): Effects on Properties and Ion-Exchange Capacity Estimation[END_REF][START_REF] Mashtalir | Intercalation and delamination of layered carbides and carbonitrides[END_REF] . The introduction of the proper molecules can induce swelling of the interlayer space and a concomitant weakening of the inter-layer interactions which, as noted above, is key to exfoliating multilayers into single nanosheets on a large scale. Additional energetic treatments, such as sonication or shaking, can also lead to the exfoliation of MXenes and their dispersion in water or other solvents (see Figure 4 A).

The polar organic molecule dimethyl sulfoxide (DMSO) has been used to exfoliate Ti3C2Tz 70 and (Mo2/3Ti1/3)3C2Tz [START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF] . Expansion of the interlayer space is evidenced by a shift to lower angle 2θ of the (00l) peaks in X-ray diffraction (XRD) patterns. Note that the position of the (0002) peaks in the XRD patterns corresponds to half the c lattice parameter and is henceforth referred to simply as the interlayer d-spacing. For example, the intercalation of DMSO results in an increase of the d-spacing in Ti3C2Tz from 9.8 Å to 17.6 Å (see Figure 4 B) [START_REF] Mashtalir | Intercalation and delamination of layered carbides and carbonitrides[END_REF] . The d-spacing can even increase further to 22.4 Å with the co-intercalation of water. For reasons that are not completely clear, apart from these two MXene compositions, DMSO is not effective for other MXenes.

However, Nb2CTz can be exfoliated via the intercalation of isopropylamine [START_REF] Mashtalir | Amine-Assisted Delamination of Nb2C MXene for Li-Ion Energy Storage Devices[END_REF] . The exfoliation using tetrabutylammonium hydroxide (TBAOH), commonly used for other 2D materials [START_REF] Omomo | Redoxable nanosheet crystallites of MnO2 derived via delamination of a layered manganese oxide[END_REF] , was first proven on V2CTz and Ti3CNTz [START_REF] Naguib | Large-scale delamination of multi-layers transition metal carbides and carbonitrides "MXenes[END_REF] . This method relies on the intercalation of TBA + ions in the interlayer space. Other large organic base molecules, such as choline hydroxide and n-butylamine were also used for V2CTz [START_REF] Naguib | Large-scale delamination of multi-layers transition metal carbides and carbonitrides "MXenes[END_REF] . TBAOH was then successfully used to exfoliate many more MXene compositions, such as (Mo2/3Ti1/3)3C2Tz and (Mo1/2Ti1/2)4C3Tz 74 , Ti4N3Tz 66 , Mo2CTz [START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF] . Interestingly, TBAOH does not exfoliate Ti3C2Tz but TMAOH does [START_REF] Alhabeb | Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti3C2Tx MXene)[END_REF] .

And while these results clearly show that different intercalants are needed to produce MXene colloidal suspensions, there are other more effective and simpler routes. A major attraction of the HCl/LiF etching methodin addition to eliminating HF and its hazardsis that it not only etches the Al layer, but enables the, almost simultaneous, exfoliation of the multilayers by the introduction of Li + and its water of hydration in the interlayer space (see Figure 4 A). The d-spacing of dry multilayers obtained with the HCl/LiF method is close to 13 Å, at least 3 Å larger than multilayers etched with HF alone [START_REF] Ghidiu | Conductive two-dimensional titanium carbide 'clay' with high volumetric capacitance[END_REF] (see Figure 4 B). When the multilayers are wet, viz. never dried, and then exposed to water the d-spacing expands to 16.5 Å, and this co-intercalation of water facilitates the eventual exfoliation [START_REF] Ghidiu | Ion-Exchange and Cation Solvation Reactions in Ti3C2 MXene[END_REF] . Indeed, after washing multilayers etched with the HCl/LiF mixture to a pH of ~6, spontaneous exfoliation is observed [START_REF] Ghidiu | Conductive two-dimensional titanium carbide 'clay' with high volumetric capacitance[END_REF] . The yields can be increased with the help of sonication. Using the HCl/LiF method, Lipatov et al. [START_REF] Lipatov | Effect of Synthesis on Quality, Electronic Properties and Environmental Stability of Individual Monolayer Ti3C2 MXene Flakes[END_REF] showed that increasing the initial molar ratio of LiF:Ti3AlC2 from 5:1 to 7.5:1 resulted in an increase of the yield of exfoliation by hand shaking.

After exfoliation, colloidal nanosheet suspensions, if they are not to be used immediately, have to be stabilized to prevent their aggregation by using adequate solvents and/or surfactants.

Arguably, one of the reasons MXenes have become so popular lately (more than 400 papers published in 2018 alone) has to be the ease by which water stable colloids near neutral pH can be produced. Note when the pH veers significantly from neutral, the suspensions are no longer stable [START_REF] Natu | Mesoporous MXene powders synthesized by acid induced crumpling and their use as Na-ion battery anodes[END_REF][START_REF] Zhao | Alkali-induced crumpling of Ti3C2Tx (MXene) to form 3D porous networks for sodium ion storage[END_REF] . Maleski et al. studied the stabilities of exfoliated MXenes in various organic solvents, and showed that in general polar solvents are better at dispersing Ti3C2Tz than non-polar ones [START_REF] Maleski | Dispersions of Two-Dimensional Titanium Carbide MXene in Organic Solvents[END_REF] .

As generally the case with colloids, exfoliated sheets are separated from their multilayers and any unreacted parent phase by centrifugation. Once a colloidal suspension of single or few sheets is obtained it can be processed in a variety of different ways (Figure 4 C): vacuum filtration to obtain thick films (typically a few microns) with orientated flakes [START_REF] Mashtalir | Intercalation and delamination of layered carbides and carbonitrides[END_REF] , crashed by the addition of an acid or a base to obtain an open crumpled morphology [START_REF] Natu | Mesoporous MXene powders synthesized by acid induced crumpling and their use as Na-ion battery anodes[END_REF] , spray [START_REF] Hantanasirisakul | Fabrication of Ti3C2Tx MXene Transparent Thin Films with Tunable Optoelectronic Properties[END_REF] or spin coated [START_REF] Dillon | Highly Conductive Optical Quality Solution-Processed Films of 2D Titanium Carbide[END_REF][START_REF] Ying | Transparent, conductive solution processed spincast 2D Ti2CTx (MXene) films[END_REF] to obtain thin films (below 100 nm). Because the flakes are conductive it is also possible to form relatively thick films rapidly by electrophoretic deposition [START_REF] Collini | Electrophoretic Deposition of Two-Dimensional Titanium Carbide (MXene) Thick Films[END_REF] . and illustrations of processing the solution: digital photograph on the left and SEM images of (from top to bottom) vacuum filtered film (cross section for the SEM image), crumpling powder (adapted with permission from [START_REF] Natu | Effect of Edge Charges on Stability and Aggregation of Ti3C2Tz MXene Colloidal Suspensions[END_REF] Copyright 2018 American Chemical Society) and spin-coated film (cross section for the SEM image adapted with permission from 80 , Wiley).

MXene characteristics produced by top-down synthesis

Chemical order in MXenes

As noted above, when the Al layers are etched from the o-and i-MAX, the order is, for the most part, preserved. Density functional theory (DFT) calculations predicted the stability at 0 K of 26 different type of MXenes derived from o-MAX phases [START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF] . For now, (Cr2/3Ti1/3)3C2Tz, (Mo2/3Ti1/3)3C2Tz and (Mo1/2Ti1/2)4C3Tz were obtained from their parent o-MAX phases with Ti located in the inner layers [START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF] (Figure 3), and also (Mo2/3Sc1/3)3C2Tz [START_REF] Meshkian | Theoretical stability and materials synthesis of a chemically ordered MAX phase, Mo2ScAlC2, and its two-dimensional derivate Mo2ScC2 MXene[END_REF] . Not too surprisingly, the electrochemical properties of (Mo2/3Ti1/3)3C2Tz are controlled by the outer Mo layer [START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF] . However, the inner layers also play an important role. For example, Cr2CTz MXenes has never been successfully synthesized because it tends to dissolve, but (Cr2/3Ti1/3)3C2Tz has. This implies that the inner Ti layer of (Cr2/3Ti1/3)3C2Tz improves the overall stability of the Cr outer layer during etching.

The etching of the i-MAX phases can be tuned to either only etch the Al layers or both the Al and the minority M element (Figure 2). For example, etching both Sc and Al from (Mo2/3Sc1/3)2AlC, results in the formation of Mo1.33CTz MXenes with ordered divacancies [START_REF] Tao | Two-dimensional Mo1.33C MXene with divacancy ordering prepared from parent 3D laminate with in-plane chemical ordering[END_REF] . The same composition can also be obtained from (Mo2/3Y1/3)2AlC, when Y is etched together with Al [START_REF] Persson | Tailoring Structure, Composition, and Energy Storage Properties of MXenes from Selective Etching of In-Plane, Chemically Ordered MAX Phases[END_REF] . Following the same method, W1.33CTz was obtained from the i-MAX phases (W2/3Sc1/3)2AlC and (W2/3Y1/3)2AlC [START_REF] Meshkian | W-Based Atomic Laminates and Their 2D Derivative W1.33C MXene with Vacancy Ordering[END_REF] . These ordered divacancies influence MXene properties: for instance, Mo1.33CTz exhibits a 65 % higher volumetric capacitance than its counterpart with no vacancies, viz. Mo2CTz. Interestingly, by controlling the etching conditions of (Mo2/3Y1/3)2AlC powders, only the Al layer can be etched resulting in a MXene with in-plane ordering of the two transition metal elements [START_REF] Persson | Tailoring Structure, Composition, and Energy Storage Properties of MXenes from Selective Etching of In-Plane, Chemically Ordered MAX Phases[END_REF] . In case of the (Nb2/3Sc1/3)2AlC phase, there is no order. It follows that when both Al and Sc are etched, the resulting in MXenes has randomly distributed vacancies [START_REF] Halim | Synthesis of Two-Dimensional Nb1.33C (MXene) with Randomly Distributed Vacancies by Etching of the Quaternary Solid Solution (Nb2/3Sc1/3)2AlC MAX Phase[END_REF] .

Surface chemistries

As noted a few time, upon etching, the A layersmostly Al -are replaced by surface terminations, mainly -OH, -O or -F groups [START_REF] Halim | X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)[END_REF] (Figure 5 A). Since some MXene properties depend on these terminations [START_REF] Dall'agnese | High capacitance of surface-modified 2D titanium carbide in acidic electrolyte[END_REF] , it is essential to know their nature and relative amounts. The multilayer terminations will depend on the: (i) etching method, (ii) nature of the M and X elements and, (iii) number of MX layers, or n. Fluorine-free MXenes can be obtained by the hydrothermal treatment of Ti3AlC2 powders in NaOH [START_REF] Li | Fluorine-Free Synthesis of High-Purity Ti3C2Tx (T=OH, O) via Alkali Treatment[END_REF] . The electrochemical etching of Ti2AlC in diluted HCl [START_REF] Sun | Electrochemical etching of Ti2AlC to Ti2CTx (MXene) in low-concentration hydrochloric acid solution[END_REF] and Ti3AlC2 in a binary aqueous electrolyte (NH4Cl + TMAOH) [START_REF] Yang | Fluoride-Free Synthesis of Two-Dimensional Titanium Carbide (MXene) Using A Binary Aqueous System[END_REF] also yield MXenes without F terminations. To date no method has been published to synthesize MXenes terminated solely by F-terminations, or without any termination at all, the latter very unlikely except possibly under extreme reducing or vacuum conditions. X-ray photoelectron spectroscopy (XPS) analysis on a wide range of MXenes multilayers (Ti2CTz, Ti3C2Tz, Ti3CNTz, Nb2CTz and Nb4C3Tz) by Halim et al. showed that initially, after etching, most of the terminations are -F, but with time are replaced by -OH [START_REF] Halim | X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)[END_REF] . In the case of the Ti-based MXenes changing n from 1 to 2 or changing the X from C to N does not affect the quantity of -F terminations, but affects the -OH to -O termination ratio. Indeed, increasing n from 1 to 2 induces an increase in the -O to -OH ratio. Replacing half of the C atoms with N leads to a decrease in the -O to -OH ratio. The trends observed in Ti-based MXenes are different than their Nb-based counterparts. The amount of -F terminations is also affected by n and the -O to -OH ratio decreases between Nb2CTz and Nb4C3Tz (n from 2 to 4) [START_REF] Halim | X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)[END_REF] .

The MXene terminations can also be modified during the exfoliation process. For example, TBAOH, used for delaminating HF-etched MXenes, increases the -O terminations at the expense of -F 91 , indicating once again that the latter are thermodynamically unstable compared to -O. This was also observed when K + and DMSO were intercalated in the interlayer space prior to exfoliation [START_REF] Dall'agnese | High capacitance of surface-modified 2D titanium carbide in acidic electrolyte[END_REF] .

Post-synthesis of the MXene surface chemistry is also possible. For example, in situ heating, while collecting XPS spectra of Ti3C2Tz thin films showed that the -F terminations start to desorb around 500 °C and are mostly desorbed by 750 °C [START_REF] Persson | On the organization and thermal behavior of functional groups on Ti3C 2 MXene surfaces in vacuum[END_REF] (Figure 5 C). Thermal annealing of Ti2C(OH)xFy at 1100 °C also resulted in a loss of the -F terminations and the formation of Ti2COx [START_REF] Lai | Surface group modification and carrier transport properties of layered transition metal carbides (Ti2CTx , T: -OH, -F and -O)[END_REF] . The -F terminations on MXenes multilayers can also react with alkali hydroxides and are replaced by -O or -OH terminations [START_REF] Lian | Alkalized Ti3C2 MXene nanoribbons with expanded interlayer spacing for high-capacity sodium and potassium ion batteries[END_REF] . [START_REF] Maleski | Dispersions of Two-Dimensional Titanium Carbide MXene in Organic Solvents[END_REF] , Elsevier, (B) is adapted with permission from 87 , (C) is adapted with permission from [START_REF] Persson | On the organization and thermal behavior of functional groups on Ti3C 2 MXene surfaces in vacuum[END_REF] .

Figure 5: Terminations on Ti3C2Tz. (A) Schematic view of a M3X2Tz MXene showing various terminations: I refers to a -O termination, II to -OH, III to -F and IV to -OH strongly bond to an adsorbed H2O molecule. (B) Stoichiometry of surface functional groups on Ti3C2Tz produced by etching Ti3AlC2 in HF or HCl/LiF solutions. (C) In situ XPS measurements revealing the temperature dependent behavior of (from left to right) F 1s, O 1s, and Ti 2p with heating in vacuum. (A) is adapted with permission from

Defects

Defects can originate from the parent 3D layered materials, during etching and/or exfoliation. Most of the studies done so far have focused on the influence of the etching and exfoliation methods. Not surprisingly, they show that milder conditions result in MXenes flakes with less defects [START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF][START_REF] Alhabeb | Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti3C2Tx MXene)[END_REF][START_REF] Lipatov | Effect of Synthesis on Quality, Electronic Properties and Environmental Stability of Individual Monolayer Ti3C2 MXene Flakes[END_REF][START_REF] Sang | Atomic Defects in Monolayer Titanium Carbide (Ti3C2Tx) MXene[END_REF] .

At the atomic scale, intrinsic defects have been observed in single or double layers of Ti3C2Tz by TEM. Figure 6 A, shows metal adatoms and vacancies [START_REF] Karlsson | Atomically Resolved Structural and Chemical Investigation of Single MXene Sheets[END_REF][START_REF] Sang | Atomic Defects in Monolayer Titanium Carbide (Ti3C2Tx) MXene[END_REF] , where in this case the Ti adatoms are positioned above other Ti atoms in the MXene lattice. Karlsson et al. [START_REF] Karlsson | Atomically Resolved Structural and Chemical Investigation of Single MXene Sheets[END_REF] suggested that Ti adatoms react with oxygen to form TiOx complexes. Modifying the etching method also has an impact on the metal vacancies. It was shown that increasing the HF concentration during etching results in an increase in the defect concentration [START_REF] Sang | Atomic Defects in Monolayer Titanium Carbide (Ti3C2Tx) MXene[END_REF] .

Defects at the macroscopic scale, such as pores, were observed in MXene single layers and also depend on the etching conditions. For instance, it was shown that shorter etching times resulted in less defective Mo2CTz flakes, but the MAX to MXenes conversion efficiency was lower [START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF] . Sonication during exfoliation can increase the yield, but the resulting flakes are more defective with a higher porosity as evidenced in Mo2CTz in Figure 6 B, and are smaller as shown on Ti3C2Tz in Figure 6 C. When a milder method is used, such as hand-shaking, the flakes are bigger (Figure 6 C) [START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF][START_REF] Lipatov | Effect of Synthesis on Quality, Electronic Properties and Environmental Stability of Individual Monolayer Ti3C2 MXene Flakes[END_REF] . Defects free single MXene layers have still not been reported to our knowledge. [START_REF] Karlsson | Atomically Resolved Structural and Chemical Investigation of Single MXene Sheets[END_REF] , Copyright 2015 American Chemical Society. (B) is adapted with permission from [START_REF] Halim | Synthesis and Characterization of 2D Molybdenum Carbide (MXene)[END_REF] , Wiley. (C) is adapted with permission from [START_REF] Anasori | 2D metal carbides and nitrides (MXenes) for energy storage[END_REF] , Copyright 2017 Springer Nature.

Figure 6: Defects in MXene single layers. (A) Atomic defects in Ti3C2Tz: single Ti vacancy in a double sheet (left), Ti adatom on a single sheet (right). (B) Mo2CTz sheets after etching in HF, intercalation with TBAOH and delaminated by two methods: hand shaking for 5 min (left) or sonication during 1 h (right). (C) Synthesis of Ti3C2Tz by two methods: route 1 with exfoliation by sonication leads to smaller flakes size, while route 2 with exfoliation by hand shaking gives larger flakes size. (A) is adapted with permission from

Synthesis of 2D transition metal carbides and nitrides by bottom-up approaches

As shown above, selective etching methods have been extensively used to synthesize MXenes. Recently, several bottom-up synthesis methods have also been developed including chemical vapor deposition (CVD) [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF][START_REF] Gogotsi | Chemical vapour deposition: Transition metal carbides go 2D[END_REF][105][106][107][START_REF] Geng | Controlled growth of ultrathin Mo2C superconducting crystals on liquid Cu surface[END_REF][START_REF] Wang | Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides[END_REF][START_REF] Qi | Unique Transformation from Graphene to Carbide on Re(0001) Induced by Strong Carbon-Metal Interaction[END_REF][100][101][102][103][104] , template method 108-110 and plasma enhanced pulsed laser deposition (PEPLD) 111,112 . Compared to the selective etching process, the materials produced by the bottom-up methods, in particular CVD, have high crystalline quality. Moreover, these methods enable the synthesis of 2D transition metal carbides (TMCs) and nitrides (TMNs) with stoichiometries that cannot be obtained by selective etching, such as WC [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF]103 , TaC [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF][START_REF] Wang | Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides[END_REF] , TaN [START_REF] Wang | Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides[END_REF] , MoN 108,109 and heterostructures [100][101][102][103][104][105]107 . It is important to note that neither single layers of TMCs or TMNs have been grown so far with these methods, but rather thin film comprised of a few layers. However, the thin films exhibit 2D properties, in terms of superconducting transitions for example [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF] .

CVD growth of 2D TMCs and TMNs

In 2015, Xu et al. [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF] first reported the growth of high-quality ultrathin TMCs crystals by CVD, in which a bilayer metal foil (copper, Cu/transition metal) was used as a growth substrate.

A schematic of the CVD growth process is shown in Figure 7 A 113 . The stack of Cu/Mo foils was first heated to a temperature above 1085 C (Cu melting point) in hydrogen (H2), and then a low flow rate of methane was introduced, resulting in the formation of Mo2C crystals on the liquid Cu surface. During the growth process, the top liquid Cu layer plays several important roles. On the one hand, it acts as catalyst to decompose methane into carbon atom. On the other hand, it works as a channel to control the diffusion of Mo atoms from the Mo foil to the liquid Cu surface. As a result, ultrathin Mo2C crystals are formed on the liquid Cu surface by the reaction of C and Mo atoms. In addition, after Mo2C growth, the Cu acts as a sacrificial layer that, in turn, enables the transfer of Mo2C to any target substrate by etching because of the large differences in chemical reactivity between Cu and Mo2C.

Figure 7 B shows a typical ultrathin Mo2C crystals grown on a Cu/Mo substrate. The latter appear in various regular shapes, mainly including triangles, rectangles, hexagons, octagons, nonagons and dodecagons. The thickness of most crystals can be controlled within 3-20 nm. Importantly, the crystals can be transferred perfectly onto arbitrary target substrates by using 0.2 M (NH4)2S2O8 solution to etch the Cu. Atomic force microscopy (AFM) images show that the Mo2C crystals have clean and smooth surfaces (Figure 7 C). Selective area electron diffraction (SAED) was used to show that the crystal structure was orthorhombic, α-Mo2C (Figure 7 D). Different from MXenes, atomic-level high angle annular dark field (HAADF)scanning transmission electron microscope (STEM) measurements show that the as-obtained α-Mo2C crystals have a high crystalline quality (Figure 7 E). These high-quality samples provide a good platform to study the intrinsic properties of TMCs near the 2D limit, such as 2D superconductivity [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF]114,115 .

Further studies 116 show that the Mo atom sub-lattice has uniform hexagonal closelypacked arrangement across the crystal without boundaries for all shaped crystals. However, except for the rectangular and octagonal crystals, the C atom sub-lattices are composed of three or six domains with rotational-symmetry and well-defined line-shaped domain boundaries because of the presence of three equivalent octahedron-off-center zigzag configurations of C atoms, as shown in Figure 7 F-I. These domain boundaries have been shown to have a strong influence on the 2D superconductivity. Moreover, the 2D α-Mo2C crystals can be transformed into β-Mo2C crystals under electron irradiation in a TEM 117 . Importantly, this CVD method is quite universal and can also be used to grow other high quality 2D TMC crystals such as ultrathin hexagonal WC (Figure 7 J and K) and cubic TaC (Figure 7 L and M). The latter are grown using W and Ta foils instead of Mo, respectively [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF] . Following this work, Geng et al. [START_REF] Geng | Controlled growth of ultrathin Mo2C superconducting crystals on liquid Cu surface[END_REF] demonstrated structural control of the morphology of Mo2C crystals by changing the concentration of CH4. When a low flow rate of CH4 (0.1 sccm) was used, fractal Mo2C crystals were obtained. With increasing CH4 concentration, the shape of Mo2C crystals changed from triangular to other polygons, resulting from a higher C supersaturation. At CH4 flow rates of 0.3 sccm, 0.4 sccm and 0.6 sccm, the dominant shapes were rectangles, pentagons and hexagons, respectively. However, they found that the hexagonal Mo2C crystals have a hexagonal structure, which is different from the orthorhombic structure reported by Xu et al. [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF] Furthermore, they realized that the thickness of the Mo2C crystals can be controlled by changing the thickness of the Cu foil. Very recently, Chaitoglou et al. 104 reported the growth of stacks of Mo2C crystals with a thickness of ~ 2 nm, which demonstrates the 2D limit of the Mo2C domains. 113 , (B-E, J-M) are adapted with permission from Springer Nature [START_REF] Xu | Large-area high-quality 2D ultrathin Mo2C superconducting crystals[END_REF] Copyright 2015, (F-I) are adapted with permission from 116 Copyright 2016 American Chemical Society, (N, O) are adapted with permission from [START_REF] Wang | Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides[END_REF] Copyright Wiley-VCH.

(J,K) Optical (J) and HRTEM (K) images of the 2D ultrathin hexagonal WC crystals. (L,M) Optical (L) and HRTEM (M) images of the 2D ultrathin cubic TaC crystals. (N) Schematic of the CVD growth of ultrathin 2D TaC crystals. (O) HRTEM image of 2D TaN crystal. The inset of (O) is the SAED pattern along [001]. (A) is adapted with permission from

CVD growth of Heterostructures of 2D TMCs and Graphene

In addition to 2D TMC and TMNs, CVD methods can also be used directly to synthesize vertical/in-plane heterostructures of graphene and 2D TMCs 100-105,107 . Two different synthesis approaches have been reported to grow 2D Mo2C/graphene vertical heterostructures. Deng et al.

reported the direct growth of such structures using one-step CVD, as shown in Figure 8 A-C 107 .

Compared to the growth of pure Mo2C crystals, a higher concentration of CH4 was used to form graphene. The visible Raman D peak indicates the presence of defects in the graphene in the heterostructures which is possibly because of a competition between the growth of the 2D Mo2C crystals and the graphene. The 2D Mo2C crystals are located on the top of the graphene layers. Moreover, a 2D spinodal interface was observed, which indicates that the interface in this onestep CVD grown heterostructure is not perfect (Figure 8 E) 105 . Different from Loh's work 100 , they found that the 2D Mo2C is located on the bottom of the graphene layers in all their heterostructures synthesized by one-step CVD 101,105,107 . Xu et al. 102 developed a two-step CVD method to grow graphene/2D Mo2C vertical heterostructures, in which the 2D Mo2C is located at the bottom of the graphene layer. As shown in Figure 8 F, an intact graphene film was first grown on a solid Cu surface at temperature below the melting point of Cu. Subsequently, the growth temperature was increased to above the melting point to grow Mo2C crystals underneath the graphene layer on the liquid Cu surface.

Very interestingly, as shown in Figure 8 G and H, the graphene and Mo2C crystals are well aligned in lattice orientation in the heterostructures, suggesting epitaxial growth of Mo2C on graphene. Similar to the pure Mo2C crystals alluded to above, the Mo2C crystals in the heterostructures have high crystalline quality. However, it was found that there is a considerable compression in the graphene in the heterostructure, as evidenced by the large Raman shift of both G and 2D peaks, revealing a strong coupling between graphene and Mo2C. Raman maps of the heterostructure (Figure 8 J-L) clearly show the presence of non-uniform strain domains, which results in unique superconductivity behavior that has not observed before in artificially stacked graphene/2D superconductor heterostructures. Chaitoglou et al. also confirmed the nonuniform stress in heterostructures by using Raman spectroscopy 104 .

Besides vertical heterostructures, 2D in-plane TMC-graphene (i-WC-G) heterostructure can also be synthesized by a similar CVD process. Zeng et al. 103 synthesized 2D in-plane WCgraphene heterostructures at 980-1020 C, using a substrate of a Ga droplet sitting on the top of a W foil (Figure 8 M). They explained that Ga, as a low melting point metal, provides the possibility for co-segregation of W and C atoms to form in-plane WC-graphene heterostructure.

As shown in Figure 8 N, 2D WC crystals were uniformly embedded in graphene film. The coverage percentage of WC can be controlled from 40% to 95% by changing the growth parameters, including growth temperature and growth time. The WC crystals also have a high quality and a typical hexagonal crystalline structure (Figure 8 O). Moreover, based on AFM measurements they were ~1.36 nm thick (Figure 8 P).

PEPLD Methods for the Synthesis of 2D TMCs

Recently, Zhang et al. 111,112 developed a PEPLD method to synthesize large-area ultrathin, FCC Mo2C films on sapphire (0001). This approach combines the advantages of both plasma enhanced chemical vapor deposition and pulsed laser deposition. In this synthesis process, the sapphire substrate was heated to 700 C for the deposition of high quality Mo2C film, using CH4 plasma as a C source reacted with the Mo vapor generated by the pulsed laser.

They found that CH4 plasma favors the formation of Mo2C. The as-obtained FCC Mo2C film is quite uniform and smooth, as shown in Figure 9 L and can be controlled within 2-25 nm by changing the laser pulse rate. However, the films obtained have much lower crystalline quality than the CVD-grown samples, and a large number of stacking faults were observed in cross sectional TEM images (Figure 9 M). They suggested that the formation of the FCC structure unlike other crystal structures originates from an orientation relationship and little lattice mismatch between {111}Mo2C and {0003}sapphire (Figure 9 N).

Conclusion

Currently about 30 different MXene compositions have been synthesized by top-down approaches and theoretical studies predict the stability of many more. New MXenes are being discovered regularly, as well as new etching methods. Ironically, this embarrassment of richness poses somewhat of a dilemma. To date, and as this review attests, the vast majority of MXene papers have been on the first MXene discovered, viz. Ti3C2Tz. And while this composition has already shown great promise in a large number of applications, there is no reason to believe it is the best for all applications. There is therefore an urgent need to bring our understanding of other compositions to the same level as Ti3C2Tz. This is a non-trivial exercise given the large number of compositions and possible termination permutations, defects, etc. This is made even more urgent by the fact that even for Ti3C2Tz there is a lot more we do not understand than we understand.

The most efficient way to obtain this wide variety of MXenes is to use HF for now. An important challenge is to develop etching protocols without HF not only because of its toxicity, but also because the MXenes produced using HF contain -F terminations which are problematic for some applications, especially in the biomedical field. Even if -F terminations are reported to be less stable than -O and -OH, there has been no report so far for their simple conversion post synthesis.

The discovery that LiF/HCl mixtures etched Ti3AlC2 was an important breakthrough since for the most part it eliminated the direct use of HF. However, HF is still produced in-situ, and is present in the resulting etching solutions, and needs to be washed and processed. Li et al. [START_REF] Li | Fluorine-Free Synthesis of High-Purity Ti3C2Tx (T=OH, O) via Alkali Treatment[END_REF] were the first to show that it is possible to etch Ti3AlC2 hydrothermally without fluoride ions, but the requisite conditions (270 °C in an autoclave) are quite harsh, not scalable and the properties of the resulting flakes have yet to be thoroughly investigated. The approach taken by Sun et al. [START_REF] Sun | Electrochemical etching of Ti2AlC to Ti2CTx (MXene) in low-concentration hydrochloric acid solution[END_REF] in which porous MAX preforms were electrochemically etched in HCl is worth noting here. However, at this time, the yields of this method are quite low and the process quite slow indeed. A promising method is very recent work published by Yang et al. [START_REF] Yang | Fluoride-Free Synthesis of Two-Dimensional Titanium Carbide (MXene) Using A Binary Aqueous System[END_REF] : they not only converted Ti3AlC2 in Ti3C2Tz electrochemically in a F-free electrolyte with yields higher than 40 %, but also showed comparable performances in supercapacitors of the resulting MXenes to those obtained using the classical HF or HCl/LiF methods.

The timing of the discoveries of the i-MAX and o-MAX phases could not have been better vis-à-vis greatly expanding MXene's chemical and structural space. It is worth noting that these phases, especially the i-MAX phases and their MXenes are still in their infancy and it is reasonable to assume that many more "ordered" MXenes will be discovered in the near future.

The same is true of the o-MAX phases: DFT calculations predict the existence of 26 MXenes derivable from these phase [START_REF] Anasori | Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)[END_REF] . Only a small fraction of their parent MAX phases has been synthesized. Discovering these phases, converting them to their MXenes, characterizing them and matching them with the myriad applications is a daunting, but exciting proposition. The same is true for the i-MAX phases. The importance of the latter lies in the possibility of introducing non-traditional M elements into the mix. The original M elementsdiscovered by Nowotny -were: Ti, V, Cr, Zr, Nb, Mo, Hf and Ta. Interestingly before 2014, only one Mocontaining MAX phase was known, today there are five.

As noted in the introduction the MXene discovery was paradigm shifting, because it showed the 3D to 2D transformation is not only restricted to relatively weakly bonded layered solids. For example, Zhou et al. have shown that it is possible to etch layered solids that are not MAX phases [START_REF] Zhou | A Two-Dimensional Zirconium Carbide by Selective Etching of Al3C3 from Nanolaminated Zr3Al3C5[END_REF][START_REF] Zhou | Synthesis and Electrochemical Properties of Two-Dimensional Hafnium Carbide[END_REF] . By etching Al3C3 and (Al,Si)4C4 from Zr3Al3C5 and Hf3(Al,Si)4C6, respectively, they produced the first Hf and Zr-based MXenes.

Besides the well-known selective etching method, several bottom-up synthesis methods have been developed to synthesize 2D TMCs and TMNs. The CVD method, with bilayer metal foils as substrate, not only enables the growth of large-area, high-quality materials but also greatly expands the family of 2D TMCs and TMNs. Various 2D TMCs and TMNs, including MX-type (WC, TaC and TaN), non-hexagonal M2X-type (α-Mo2C, fcc-Mo2C) and hexagonal M2X-type (β-Mo2C) have been synthesized by CVD. Moreover, the CVD process is also an effective method for the growth of vertical and in-plane heterostructures of 2D TMCs and graphene. The template method shows great potential to synthesize uniform atomically thin nanosheets at a large The PEPLD method can also be used to grow large-area films.

However, there are still many issues and challenges needed to be addressed for these bottom-up methods. For example, synthesizing large-area, high-quality atomically thin uniform 2D TMCs and TMNs film by CVD still remains a great challenge, and the materials synthesized by template and PEPLD methods have visible defects.

Figure 1 :

 1 Figure 1: Pathway to obtain 2D MXene single flakes by top-down synthesis. (A) to (B): First, selective etching of atomic layer(s) from a 3D layered precursor is required ((A) is a scanning electron microscope (SEM) micrograph of Ti3AlC2 particles. (B) SEM picture of Ti3C2Tz multilayer after etching of the Al layer. (C): Transmission electron microscope (TEM) micrograph of overlapping Ti3C2Tz single layers. Schematics of the MAX to multilayers MXene transformation and their exfoliation are shown in bottom row.

Figure 2 :

 2 Figure 2: The MXene familypart 1/2. Summary of existing MXenes with M1.33XTz and M2XTz compositions. Precursors, etching method used to obtain them, and highlights are shown.

Figure 3 :

 3 Figure 3: The MXene familypart 2/2. Summary of MXenes with M3X2Tz and M4X3Tz compositions.

Figure 4 :

 4 Figure 4: Exfoliation of multilayers MXenes into 2D nanosheets. (A) Schematic for MXenes exfoliation process depending on the etching process. (B) XRD patterns for Ti3AlC2 MAX phase (blue), dry multilayers Ti3C2Tz MXenes after etching with HF and washing (green) and after intercalation with DMSO (orange), dry (solid line purple) and wet (dotted line purple) multilayers Ti3C2Tz MXenes etched with HCl + LiF. (C) Picture of a colloidal suspension of exfoliated MXenes showing the Tyndall effect

  Quantitative nuclear magnetic resonance (NMR) spectroscopy has shown that multilayers Ti3C2Tz obtained by the HF etching method exhibit almost four times more -F terminations than ones etched in HCl/LiF (Figure 5 B) 87 . MXenes obtained by both methods have significantly fewer -OH terminations than -F and -O. Kajiyama et al. claimed that Ti2CTz MXenes etched using HCl + LiF possibly have -Cl terminations, and further claimed that these terminations increase the d-spacing due to steric repulsion 88 . Recent work by Voigt et al. showed that Ti3C2Tz multilayers etched using a combination of HF + other acids -such as HCl, HBr, HI, H3PO4 or H2SO4 -resulted in larger interlayer spacings than if they were not used, leading them to conclude that the anions of the mineral acids adsorb along the edges of the nanosheets, keeping the interlayer space open 89 .

Figure 7 :

 7 Figure 7: 2D TMCs and TMNs synthesized by CVD. (A) Schematic of the growth process and atomic models of 2D Mo2C crystals. (B) Optical image of 2D α-Mo2C crystals on Cu/Mo substrate. (C) AFM image of a 8.2 nm-thick α-Mo2C crystal transferred on SiO2/Si substrate. (D) SAED pattern of α-Mo2C single crystal along [100]. (E) Atomiclevel HAADF-STEM image of α-Mo2C crystal. (F) SAED pattern of an ultrathin hexagonal Mo2C crystal. (G-I) Dark-field TEM images obtained from the ED spots 1-3 in (F) clearly showing the well-defined domain structure of the hexagonal Mo2C crystal. (J,K) Optical (J) and HRTEM (K) images of the 2D ultrathin hexagonal WC crystals.

  Qiao et al. 101,105 also synthesized vertical heterostructures of 2D Mo2C and graphene by a onestep CVD process and studied the interfacial orientational relationship between the Mo2C and graphene. A 11° rotational angle was found between the two, as shown in Figure 8 D 101 .

Figure 8 :

 8 Figure 8: The heterostructures of 2D TMCs and graphene synthesized by CVD. (A) Schematic of one-step CVD growth of 2D α-Mo2C/graphene vertical heterostructures. (B) Optical image of a hexagonal 2D α-Mo2C/graphene heterostructure on Cu/Mo substrate. (C) Raman spectra of the graphene taken from the A and B areas in (b). (D) SAED pattern of 2D α-Mo2C/graphene heterostructure, in which the ED spots related to graphene and α-Mo2C are marked by blue and green circles, respectively. The scale bar is 5 nm -1 . (E) HRTEM image of the cross section of 2D Mo2C/graphene heterostructure. (F) Schematic of the two-step CVD growth process of graphene/2D α-Mo2C vertical heterostructure. (G) Optical image of graphene/2D α-Mo2C heterostructures on growth substrate. (H) SAED pattern of a graphene/2D α-Mo2C crystal heterostructure, in which the ED spots related to graphene and α-Mo2C are marked by green circles and red spots, respectively. I) Raman spectra of a pure 2D α-Mo2C crystal, the heterostructure denoted by red circle in (J) and the pure graphene denoted by black circle. (J-L) Optical image (J) of a graphene/hexagonal 2D α-Mo2C heterostructure, and the corresponding G (K) and 2D peak (L) position maps. The scale bars are 5 μm. (M) Schematic of a Ga/W bilayer substrate for CVD growth of 2D i-WC-G. (N) SEM image of ultrathin WC crystals embedded in graphene film. (O) HRTEM image of 2D WC crystal. (P) AFM image of a 2D hexagonal WC crystal with a thickness of 1.36 nm. (A-C) are adapted with permission from 107 , (D) is adapted with

Figure 9 :

 9 Figure 9: 2D MoN and N-doped-Mo2C synthesized by template methods. (A) Schematic of the salt-assisted template synthesis process of ultrathin MoN nanosheets. (B) XRD pattern of 2D MoN nanosheets. Inset shows the Tyndall effect of the 2D MoN colloidal dispersion in water. (C) SEM image of 2D MoN nanosheets. Scale bar is 500 nm.(D) HRTEM image of the edge of an ultrathin MoN nanosheet. Scale bar is 5 nm. (E) Schematic representation of template synthesis process of 2D layers of δ-MoN. (F) Top-view SEM image of vertically aligned 2D layers of δ-MoN on FTO. (G-I) TEM image (G), the corresponding ED pattern (H) and fast Fourier transform (I) of N-Mo2C nanosheets. (J, K) SEM image (J) and the corresponding EDS mapping (K) of ultrathin MoN nanosheet. (L) AFM image of the as-grownMo2C thin film. (M) Enlarged cross-sectional TEM image. Inset shows a low magnification TEM image of Mo2C film grown on a sapphire substrate. (N) SAED pattern taken from the cross section of the Mo2C film grown at 700 C. (A-D), (E-F), (G-J) are adapted with permission from 108 , 109 , 110 respectively, Copyright 2017 American Chemical Society, (L-N) are adapted with permission from 111 Copyright 2017 American Physical Society.

Acknowledgments

The authors thank Pieralberto Collini, Joseph Halim and Michael Ghidiu for providing the SEM and TEM images, respectively, and Sankalp Kota for fruitful discussions. C. Xu, H-M. Cheng and W. Ren acknowledge the National Science Foundation of China (Nos. 51325205, 51290273, and 51521091), the Chinese Academy of Sciences (No. KGZD-EW-T06), the Strategic Priority Research Program of Chinese Academy of Sciences (XDB30000000), SYNL-T.S. K Research Fellowship, and the Youth Innovation Promotion Association of Chinese Academy of Sciences.

Wang et al. [START_REF] Wang | Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides[END_REF] demonstrated that the CVD method also can be used to grow various 2D Ta-compounds. Figure 7 N shows a schematic of the growth of ultrathin TaC crystals. Besides TaC, 2D TaN can be synthesized by using NH3 as a nitrogen source. Different from Xu el al.'s work, the Cu foil in this case, is kept in the solid state during the whole growth process, in which a temperature close to the melting point of Cu (1077 C) was used. Figure 7 O shows a HR-TEM image of TaN and the inset shows the SAED pattern, which confirms that the as-obtained TaN is single crystalline and of a high crystalline quality. Ultrathin TaB crystals were also synthesized by changing NH3 to boron powder as the B source. They pointed out that the thickness of the 2D crystals can be more easily controlled at a temperature below the melting point of Cu. Furthermore, they found that the lower temperatures were enough for supplying the excess energy of 0.03 eV required for a Ta atom to diffuse into a vacant Cu lattice site by DFT calculations (for example, kBT  129 meV at 1356 K).

Qi et al. [START_REF] Qi | Unique Transformation from Graphene to Carbide on Re(0001) Induced by Strong Carbon-Metal Interaction[END_REF] reported a different CVD process to grow ReC, which is a metastable carbide phase. They first grew graphene on Re (0001) at 903 K. Subsequently, the grown graphene was annealed at 953-1113 K and decomposed to C atoms, which were then dissolved in the Re substrate. Finally, during the cooling process, monatomic layer ReC crystals with a periodic "flower-like" superstructure were formed through C segregation from the Re substrate.

Unfortunately, the obtained 2D ReC is difficult to separate from the Re growth substrate.