MXenes
In materials science, MXenes are a class of two-dimensional inorganic compounds. These materials consist of few-atoms-thick layers of transition metal carbides, nitrides, or carbonitrides. First described in 2011, MXenes combine metallic conductivity of transition metal carbides and hydrophilic nature because of their hydroxyl or oxygen terminated surfaces.
Structure
As-synthesized MXenes prepared via HF etching have an accordion-like morphology, which can be referred to as a multi-layer MXene, or a few-layer MXene when there are fewer than five layers. Because the surfaces of MXenes can be terminated by functional groups, the naming convention Mn+1XnTx can be used, where T is a functional group.Mono transition metal MXenes
MXenes adopt three structures with one metal in the M-site, as inherited from the parent MAX phases: M2C, M3C2, and M4C3. They are produced by selectively etching out the A element from a MAX phase, or other layered precursor, which has the general formula Mn+1AXn, where M is an early transition metal, A is an element from group 13 or 14 of the periodic table, X is C and/or N, and n = 1–4. MAX phases have a layered hexagonal structure with P63/mmc symmetry, where M layers are nearly closed packed and X atoms fill octahedral sites. Therefore, Mn+1Xn layers are interleaved with the A element, which is metallically bonded to the M element.Double transition metal MXenes
MXene carbides have been synthesized that are composed of two transition metals. MXenes in this new family have the general formulas M’2M”C2, M’2M”2C3, or M’4M”C4, where M’ and M” are different transition metals. Double transition metal carbides that have been synthesized include Mo2TiC2, Mo2Ti2C3, Cr2TiC2, and Mo4VC4. In some of these MXenes, the Mo or Cr atoms are on outer edges of the MXene and these atoms control electrochemical properties of the MXenes. While, with others, such as Mo4VC4 or 4C3, the metals are randomly distributed throughout the structure in solid solutions.Divacancy MXenes
By designing a parent 3D atomic laminate, 2AlC, with in-plane chemical ordering, and by selectively etching the Al and Sc atoms, there is evidence for 2D Mo1.33C sheets with ordered metal divacancies.Synthesis
MXenes are typically synthesized by a top-down selective etching process. This synthetic route has been shown to be scalable, with no loss or change in properties as the batch size is increased. Producing a MXene by etching a MAX phase occurs mainly by using strong etching solutions that contain a fluoride ion such as hydrofluoric acid, ammonium bifluoride, and a mixture of hydrochloric acid and lithium fluoride. For example, etching of Ti3AlC2 in aqueous HF at room temperature causes the A atoms to be selectively removed, and the surface of the carbide layers becomes terminated by O, OH, and/or F atoms. MXene can also be obtained in Lewis acid molten salts, such as ZnCl2, and Cl terminal can be realized. The Cl-terminated MXene is structurally stable up to 750 °C.The MXene Ti4N3 was the first nitride MXene reported, and is prepared by a different procedure than those used for carbide MXenes. To synthesize Ti4N3, the MAX phase Ti4AlN3 is mixed with a molten eutectic fluoride salt mixture of lithium fluoride, sodium fluoride, and potassium fluoride and treated at elevated temperatures. This procedure etches out Al, yielding multilayered Ti4N3, which can further be delaminated into single and few layers by immersing the MXene in tetrabutylammonium hydroxide, followed by sonication.
The following MXenes have been synthesized to date:
2-1 MXenes: Ti2C, 2C, V2C, Nb2C, Mo2C
Mo2N, 2C, Ti2N, W1.33C, Nb1.33C, Mo1.33C, Mo1.33Y0.67C
3-2 MXenes: Ti3C2 , Ti3CN, Zr3C2 and Hf3C2
4-3 MXenes: Ti4N3, Nb4C3 , Ta4C3 , V4C3, 4C3
5-4 MXenes: Mo4VC4
Double transition metal MXenes:
2-1-2 MXenes: Mo2TiC2, Cr2TiC2, Mo2ScC2
2-2-3 MXenes: Mo2Ti2C3
Covalent Surface Modification
2D transition-metal carbides surfaces can be chemically transformed with a variety of functional groups such as O, NH, S, Cl, Se, Br, and Te surface terminations as well as bare MXenes. The strategy involves installation and removal of the surface groups by performing substitution and elimination reactions in molten inorganic salts.Intercalation and delamination
Since MXenes are layered solids and the bonding between the layers is weak, intercalation of the guest molecules in MXenes is possible. Guest molecules include dimethyl sulfoxide, hydrazine, and urea. For example, N2H4 can be intercalated into Ti3C22 with the molecules parallel to the MXene basal planes to form a monolayer. Intercalaction increases the MXene c lattice parameter, which weakens the bonding between MX layers. Ions, including Li+, Pb2+, and Al3+, can also be intercalated into MXenes, either spontaneously or when a negative potential is applied to a MXene electrode.Delamination
Ti3C2 MXene produced by HF etching has accordion-like morphology with residual forces that keep MXene layers together preventing separation into individual layers. Although those forces are quite weak, ultrasound treatment results only in very low yields of single-layer flakes. For large scale delamination, DMSO is intercalated into ML-MXene powders under constant stirring to further weaken the interlayer bonding and then delaminated with ultrasound treatment. This results in large scale layer separation and formation of the colloidal solutions of the FL-MXene. These solutions can later be filtered to prepare MXene "paper".MXene clay
For the case of Ti3C2Tx and Ti2CTx, etching with concentrated hydrofluoric acid leads to open, accordion-like morphology with a compact distance between layers. To be dispersed in suspension, the material must be pre-intercalated with something like dimethylsulfoxide. However, when etching is conducted with hydrochloric acid and LiF as a fluoride source, morphology is more compact with a larger inter-layer spacing, presumably due to amounts of intercalated water. The material has been found to be ‘clay-like’: as seen in clay materials, Ti3C2Tx demonstrates the ability to expand its interlayer distance hydration and can reversibly exchange charge-balancing Group I and Group II cations. Further, when hydrated, the MXene clay becomes pliable and can be molded into desired shapes, becoming a hard solid upon drying.Unlike most clays, however, MXene clay shows high electrical conductivity upon drying and is hydrophilic, being easily dispersed into single layer two-dimensional sheets in water without surfactants. Further, due to these properties, it can be quickly rolled into free-standing, additive-free electrodes for energy storage applications.
Material processing
MXenes can be easily solution processed in aqueous or polar organic solvents, such as water, ethanol, dimethyl formamide, propylene carbonate, etc., enabling various types of deposition via vacuum filtration, spin coating, spray coating, dip coating, and roll casting. There have been studies conducted on ink-jet printing of additive free Ti3C2Tx inks and inks composed of Ti3C2Tx and proteins.Lateral flake size often plays a role in the observed properties and there are several synthetic routes that produce varying degrees of flake size. For example, when HF is used as an etchant, the intercalation and delamination step will require sonication to exfoliate material into single flakes, resulting in flakes that are several hundreds of nanometers in lateral size. This is beneficial for applications such as catalysis and select biomedical and electrochemical applications. However, if larger flakes are warranted, especially for electronic or optical applications, defect-free and large area flakes are necessary. This can be achieved by Minimally Intensive Layer Delamination method, where the quantity of LiF to MAX phase is scaled up resulting in flakes that can be delminated in situ when washing to neutral pH.
Post-synthesis processing techniques to tailor the flake size have also been investigated, such as sonication, differential centrifugation, and density gradient centrifugation procedures. Post processing methods rely heavily on the as-produced flake size. Using sonication allows for a decrease in flake size from 4.4 μm, to an average of 1.0 μm after 15 minutes of bath sonication, down to 350 nm after 3 hours of bath sonication. By utilizing probe sonication, flakes were reduced to an average of 130 nm in lateral size. Differential centrifugation, also known as cascading centrifugation, can be used to select flakes based on lateral size by increasing the centrifuge speed sequentially from low speeds to high speeds and collecting the sediment. When this was performed, "large", "medium" and "small" flakes can be obtained. Density gradient centrifugation is also another method for selecting flakes based on lateral size, where a density gradient is employed in the centrifuge tube and flakes move through the centrifuge tube at different rates based on the flake density relative to the medium. In the case of sorting MXenes, a sucrose and water density gradient can be used from 10 to 66 w/v %. Using density gradients allows for more mono-disperse distributions in flake sizes and studies show the flake distribution can be varied from 100 to 10 μm without employing sonication.
Properties
With a high electron density at the Fermi level, MXene monolayers are predicted to be metallic. In MAX phases, N is mostly M 3d orbitals, and the valence states below EF are composed of two sub-bands. One, sub-band A, made of hybridized Ti 3d-Al 3p orbitals, is near EF, and another, sub-band B, −10 to −3 eV below EF which is due to hybridized Ti 3d-C 2p and Ti 3d-Al 3s orbitals. Said differently, sub-band A is the source of Ti-Al bonds, while sub-band B is the source of Ti-C bond. Removing A layers causes the Ti 3d states to be redistributed from missing Ti-Al bonds to delocalized Ti-Ti metallic bond states near the Fermi energy in Ti2, therefore N is 2.5–4.5 times higher for MXenes than MAX phases. Experimentally, the predicted higher N for MXenes has not been shown to lead to higher resistivities than the corresponding MAX phases. The energy positions of the O 2p and the F 2p bands from the Fermi level of Ti2CTx and Ti3C2Tx both depend on the adsorption sites and the bond lengths to the termination species.Only MXenes without surface terminations are predicted to be magnetic. Cr2C, Cr2N, and Ta3C2 are predicted to be ferromagnetic; Ti3C2 and Ti3N2 are predicted to be anti-ferromagnetic. None of these magnetic properties have yet been demonstrated experimentally.
Biological properties
Compared to graphene oxide, which has been widely reported as an antibacterial agent, Ti2C MXene shows lack of antibacterial properties. Investigations results revealed that Ti2C phase did not influenced negatively the gram-positive bacteria commonly occurring in the natural environment. Moreover, the slightly intensified growth of Bacillus sp. strain was observed in the vicinity of tested Ti2C. The SEM investigations of the preferential sites for bacteria adsorption indicated the presence of minor apoptosis for only Bacillus sp. strain, especially when the cells were located between individual sheets of the expanded Ti2C. Adsorption of bacteria cells on Ti2C resulted in changing of its zeta potential to that of bacteria cells. On the other hand, MXene of Ti3C2 MXene shows a higher antibacterial efficiency toward both Gram-negative E. coli and Gram-positive B. subtilis. Colony forming unit and regrowth curves showed that more than 98% of both bacterial cells lost viability at 200 μg/mL Ti3C2 colloidal solution within 4 h of exposure. Damage to the cell membrane was observed, which resulted in release of cytoplasmic materials from the bacterial cells and cell death. The principal in vitro studies of cytotoxicity of 2D sheets of MXenes showed promise for applications in bioscience and biotechnology. Presented studies of anticancer activity of the Ti3C2 MXene was determined on two normal and two cancerous cell lines. The cytotoxicity results indicated that the observed toxic effects were higher against cancerous cells compared to normal ones. The mechanisms of potential toxicity were also elucidated. It was shown that Ti3C2 MXene may affect the occurrence of oxidative stress and, in consequence, the generation of reactive oxygen species. Further studies on Ti3C2 MXene revealed potential of MXenes as a novel ceramic photothermal agent used for cancer therapy. In neuronal biocompatibility studies, neurons cultured on Ti3C2 are as viable as those in control cultures, and they can adhere, grow axonal processes, and form functional networks.Water purification properties
One-micron-thick Ti3C2 MXene membranes demonstrated ultrafast water flux and differential sieving of salts depending on both the hydration radius and charge of the ions. Cations larger than the interlayer spacing of MXene do not permeate through Ti3C2 membranes. As for smaller cations, the ones with a larger charge permeate an order of magnitude slower than single-charged cations.Applications
MXenes, as conductive layered materials with tunable surface terminations, have been shown to be promising for energy storage applications, composites, photocatalysis, water purification, gas sensors, transparent conducting electrodes, neural electrodes, as a metamaterial, SERS substrate, photonic diode, electrochromic device, and triboelectric nanogenerator, to name a few.Lithium-ion batteries (LIBs)
Some MXenes have been investigated experimentally thus far in LIBs. V2CTx has demonstrated the highest reversible charge storage capacity among MXenes in multi-layer form. Nb2CTx in multi-layer form showed a stable, reversible capacity of 170 mAhg−1 at 1C rate and 110 mAhg−1 at a 10C rate. Although Ti3C2Tx shows the lowest capacity among the four MXenes in multi-layer form, it can be easily delaminated via sonication of the multi-layer powder. By virtue of higher electrochemically active and accessible surface area, delaminated Ti3C2Tx paper demonstrates a reversible capacity of 410 mAhg−1 at 1C and 110 mAhg−1 at 36C rate. As a general trend, M2X MXenes can be expected to have greater capacity than their M3X2 or M4X3 counterparts at the same applied current, since M2X MXenes have the least number of atomic layers per sheet.In addition to the high power capabilities of MXenes, each MXene has a different active voltage window, which could allow their use as cathodes or anodes in batteries. Moreover, the experimentally measured capacity for Ti3C2Tx paper is higher than predicted from computer simulations, indicating that further investigation is required to ascertain the charge storage mechanism on MXene surfaces.
Sodium-ion batteries
MXenes also exhibit promising performances for sodium-based energy storage devices. Na+ should diffuse rapidly on MXene surfaces, which is favorable for fast charging/discharging. Two layers of Na+ can be intercalated in between MXene layers. As a typical example, multilayered Ti2CTx MXene as a negative electrode material showed a capacity of 175 mA h g−1 and good rate capability for electrochemical sodium-ion storage. It is possible to tune the Na-ion insertion potentials of MXenes by changing the transition metal and surface functional groups. V2CTx MXene has been successfully applied as a positive electrode material for sodium-ion storage. Porous MXene-based paper electrodes have also been reported, which exhibited high volumetric capacities and stable cycling performance, demonstrating that MXenes are promising for sodium-based energy storage devices where size matters.Supercapacitors
Supercapacitor electrodes based on Ti3C2 MXene paper in aqueous solutions demonstrate excellent cyclability and the ability to store 300-400 F/cm3, which translates to three times as much energy as for activated carbon and graphene-based capacitors.Ti3C2 MXene clay shows a volumetric capacitance of 900 F/cm3, a higher capacitance per unit of volume than most other materials, and does not lose any of its capacitance through more than 10,000 charge/discharge cycles.