Theoretical investigation of the MXene precursors MoxV4

Scientific Reports volume 13, Article number: 3271 (2023) Cite this article

570 Accesses

1 Citations

Metrics details

By first-principles total-energy calculations, we investigated the thermodynamic stability of the MAX solid solution MoxV4-xAlC3 in the 0 ≤ x ≤ 4 range. Results evidence that lattice parameter a increases as a function of Mo content, while the c parameter reaches its maximum expansion at x = 2.5. After that, a contraction is noticed. Mo occupies VI sites randomly until the out-of-plane ordered Mo2V2AlC3 alloy is formed. We employed the Defect Formation Energy (DFE) formalism to evaluate the thermodynamic stability of the alloys. Calculations show five stable compounds. At V-rich conditions and from Mo-rich to Mo-moderated conditions, the pristine V4AlC3 MAX is stable. In the region of V-poor conditions, from Mo-rich to Mo-moderated growth conditions, the solid solutions with x = 0.5, 1, and 1.5 and the o-MAX Mo2V2AlC3 are thermodynamically stable. The line profiles of the Electron Localization Function and Bader charge analysis show that the V-C interaction is mainly ionic, while the Mo-C is covalent. Also, the exfoliation energy to obtain a MXene layer is ~ 0.4 eV/Å2. DFE also shows that MXenes exfoliated from the MAX phase with the same Mo content and atomic arrangement are thermodynamically stable. Our results get a deeper atomic scale understanding of the previously reported experimental evidence.

The MAX compounds are a family of hexagonal layered early-transition metal carbides, nitrides, or carbonitrides with general formula Mn+1AXn1, where M is an early-transition metal, A is typically an atom of the group 13 to 16, and X is carbon/nitrogen, with n = 1, 2, and 3. Depending on the number of M layers, the shorthand notation can be 211, 312, 413, with n = 1, 2, or 3, respectively. Also, in the last years, the higher order MAX compounds (n > 3) have been successfully synthesized, such as Ti7SnC62, Ta6AlC53, (Ti0.5Nb0.5)5AlC44, (V0.5Cr0.5)5Al2C35 and Mo4VAlC46. The MAX compounds exhibit a combination of metallic and ceramic properties. They have high electrical and thermal conductivity and tribological properties. They are machinable, and present high damage tolerance and thermal-shock resistance. Also, their strength remains at high temperatures7,8,9,10,11,12,13. Thanks to their properties, the MAX compounds can be employed in catalysis14,15, in nuclear reactors16,17, and, as high-temperature protective coatings18. The MAX compounds with Al as an A element, such as Ti2AlC, Cr2AlC, and Ti3AlC2, are good candidates for high-temperature applications since they provide high oxidation resistance and form a protective alumina layer (Al2O3)19,20,21. Also, MAX compounds are the precursors of the two-dimensional MXenes discovered in 201122,23.

The Mxenes are exfoliated from the precursor MAX phase by selectively etching the A element. They possess excellent properties making them suitable materials for many applications. In the past year, the first evidence of ferroelectricity and multiferroicity in Mxenes at room temperature was obtained24. For hydrogen production through water splitting, the bifunctional catalysts Mo2TiC2 and Mo2Ti2C3 have demonstrated outstanding performance in alkaline media25. The Ti4C3 Mxene is an electrode for carbon-supported memory applications based on Ti4C3/graphene oxide/Ti4C3 frameworks26, with excellent retention and endurance characteristics. About energy storage devices, the double-ordered alloy Ti2Ta2C3 is an efficient electrode in Li-ion batteries, better than the pristine Ti4C3 Mxene27,28. Also, some reports suggest improved storage properties of the Mxenes by combining them with ZrO2, MnO2, and metallic dopants, such as Ni. In some cases, the modified materials can double the capacitance compared to pristine materials. Also, their capacitance is larger than 81% up to 10,000 cycles29,30,31.

Since the discovery of the Cr2TiAlC2 ordered structure by Liu et al.32 in 2014 -Ti is sandwiched between two chromium carbide layers in a 312 structure-, a new subclass of MAX compounds with formula (M, M’)n+1AlXn has attracted attention thanks to their chemical versatility. In the last few years, Cr- and Mo-based MAX have been synthesized with small amounts of Fe or Mn to improve their magnetic properties33,34.

In the case of the 211 MAX compounds, the alloys are in-plane (i-MAX) ordered, where the M element forms hexagons and the M’ element is at the center. An example of this is the (Mo2/3Sc1/3)2AlC MAX alloy synthesized in 201735,36. In the last years, the (V2/3Zr1/3)2AlC, (Cr2/3Sc1/3)2AlC, (Cr2/3Sc1/3)2GaC, (W2/3Sc1/3)2AlC, (Mn2/3Sc1/3)2GaC i-MAX compounds have been successfully growth1. Furthermore, in 312 and 413 MAX phases, the out-of-plane ordering is the most common (o-MAX). M’ is placed at the center of the carbide or nitride layer, forming an octahedral coordination with the C (N) atoms, while the M element appears in most exposed layers. In the last years, the o-MAX Mo2TiAlC2 and Mo2TiAlC2 have been synthesized. In both cases, Mo occupies the most exposed carbide layers, and Ti is at the inner layers37,38. This behavior has been investigated by theoretical calculations, demonstrating that Mo avoids face-centered cubic (FCC) stackings when coordinated with C since there is energy loss when adopting this configuration39.

Although the out-of-plane arrangement is the most common in the 312 and 413 double transition metals (DTM) MAX, the formation of solid solutions is another possibility. Griseri et al.40 synthesized Ta-based 413 MAX solid solutions with Hf and Nb to form (Ta1-xHfx)4AlC3 and (Ta1-xNbx)4AlC3 with x = 0.05, 0.1, 0.15, 0.2 and 0.25, they included Hf in the structure to form ultra-high temperature ceramics, as previously predicted by DFT calculations41,42. Qu and coworkers43, by Spark Plasma Sintering (SPS), obtained the (Ti1-xZrx)3SiC2 solid solution, x ranging up to 0.17. They found an anisotropic expansion of the cell parameter as Zr content increases. Recently, Pinto et al.44 synthesized for the first time the solid solution MoxV4-xAlC3 with x = 1, 1.5, 2, and 2.7. For concentrations larger than x = 2.7, the compound obtained was not identified as the MAX phase. The XRD pattern shows lattice parameters' linear expansion -as a function of Mo content- for the entire range of Mo content. However, in this report, a detailed characterization of the atomic arrangement is still needed. After that, MXenes were obtained by selective topochemical etching. Finally, the MXene layers were applied in energy storage devices, obtaining good results. Motivated by the findings of Pinto et al.44, in this work, we investigated the atomic arrangements of the MoxV4-xAlC3 solid solutions considering the entire range of concentrations (from x = 0 to x = 2). Our results show that Mo occupies V sites in a semi-ordered arrangement until reaching the Mo2V2AlC3 o-MAX. The manuscript is organized as follows: section II is for the computational methodology, the results are presented in section III, and conclusions are made in section IV.

Through a systematic computational assessment, we investigated the binary MAX alloy MoxV4-xAlC3 with 0 ≤ x ≤ 4. Calculations were performed within the periodic Density Functional Theory (DFT) as implemented in the Vienna Ab initio Simulation Package (VASP)45,46,47,48. Exchange–correlation energies are approximated using the generalized gradient approximation (GGA) and the Perdew-Burke-Ernzerhof (PBE) parametrization49. Electronic states are treated as a plane-waves with an energy cutoff of 460 eV. The frozen core approximation has been employed through the projector-augmented-wave (PAW) method50,51. Van der Waals forces were considered in the calculations employing the DFT-D3 method of Grimme52,53. Geometry optimization is achieved when all force components are less than 0.01 eV/Å, and the energy differences less than 1 × 10–4 eV. A 3 × 3 × 1 supercell has been considered to investigate the different V: Mo stoichiometries. To sample the Brillouin zone, we used the equally spaced k-points scheme of Monkhorst–Pack54, with a k-points grid of 3 × 3 × 2. The Climbing Image Nudged Elastic Band (CI-NEB) method55,56 is employed to calculate the exfoliation energy, considering seven intermediate images from the initial to final stages.

We are interested in evaluating the thermodynamic stability of the binary MAX MoxV4-xAlC3 compound, with 0 ≤ x ≤ 4. The total energy criterion is not enough since each V:Mo relationship has different number of atoms and chemical species. Therefore, we must employ the Defect Formation Energy (DFE) formalism57,58,59,60 which is independent of the number of atoms in the system and only depends on the chemical potentials of the constituent species. Thermodynamic equilibrium is required to apply the formalism, this implies:

where, μi is the chemical potential of the ith species and \({\Delta H}_{{V}_{4}Al{C}_{3}}^{f}\) is the formation enthalpy. The DFE formalism can be write as follows:

where, \({E}^{slab}\) is the total energy of the system at hand, VUC is the volume of the unit cell, and ni is the number of atoms of the ith species. V thermodynamic limit is defined by the heat of formation of the V4AlC3 MAX with:

also, the variation of the Mo chemical potential is limited by:

with \({\mu }_{Mo}^{cohesive}\) as the cohesive energy of Mo.

To investigate the thermodynamic stability of the MoxV4-xAlC3 solid solution, we choose the previously reported α-V4AlC3 MAX compound61 as the basis for the Mo substitutions. α-V4AlC3 (from now on V4AlC3) has space group P63/mmc with lattice parameter a = 2.92 Å and c = 22.75 Å. V atoms occupy 4f. (1/3, 2/3, 0.05441) and 4e (0, 0, 0.15481) Wyckoff sites, while C the 2a (0, 0, 0) and 4f. (2/3, 1/3, 0.10802) sites. Also, Al is placed in the 2c (1/3, 2/3, 1/4) Wyckoff site. Calculated MAX structure exhibits cell parameters a = 2.90 Å and c = 22.57 Å, in good agreement with experimental reports61. Figure 1a shows the V4AlC3 atomic model and its respective Density of States (DOS) (Fig. 1b), where the energy reference is the Fermi level. The structure depicts metallic characteristics. The V-3d orbitals have the most important contributions to the DOS. Each C atom is six-fold coordinated to V. Two kinds of V atoms can be distinguished: VI corresponds to the most exposed V, those that interact with Al and C atoms, and the VII that only interact with C atoms (see Fig. 1). The VII-C bond is 2.08 Å, while the bond distance between the C and the VI is ~ 1.98 Å. The Electron Localized Function (ELF) is employed to investigate the nature of the bonds present in the MAX phase, the isosurface with a value of 0.6 a.u. is shown in the Fig. S1 of the Supplementary Information (SI). The line profile across the different bonds present in the MAX is displayed in Fig. 1c. The VII-C bonds are mainly ionic. Also, the VI-C depicts a similar behavior; however, a large electron population appears in the middle of the bond, suggesting a stronger interaction, which explains the bond distances. Also, the ELF line profiles show that the VI-Al bond is the weakest, with a length of 2.71 Å. It has been reported that in the MAX compound, a weak interaction is accompanied by a strong interaction43,62. In our case, VI strongly/weakly interacts with C/Al, so delamination of the structure is possible.

(a) atomistic model of the V4AlC3 MAX compound, (b) Total and projected density of states, and (c) the line profiles of electron localization function.

Previously, it has been reported the successful synthesis of the MoxV4-xAlC3 MAX solid solution with different stoichiometries (0 ≤ x ≤ 2.7)44. By first-principles calculations and first-principles thermodynamics, we evaluated the stability of different alloys for the entire range 0 ≤ x ≤ 4. Recall that a 3 × 3 × 1 periodicity is enough to model the right stoichiometry for each case. Different atomic arrangements were considered, in which Mo is randomly placed in VI and VII sites. Also, semi-ordered arrangements were accounted for to evaluate their stability. Table 1 summarizes the relative energies of the first four stable models considered in this work for each of the different stoichiometries. Model I is the reference and the most stable configuration in all cases. See the atomistic models of the structures in Figs. S2 and S3. For the range 0 ≤ x ≤ 2, we notice that Mo substitutions have a semi-disordered arrangement, i.e., Mo randomly substitutes VI sites (see model I in Fig. S2) until they form the Mo2V2AlC3 compound. In the second place of stability are the models where Mo occupies VI sites of a single monolayer. The less stable configurations are those in which Mo randomly substitutes VI and VII sites. Note that for the Mo2V2AlC3 compound, the MAX phase adopts an out-of-plane chemically ordered structure, like Ti2Ta2C3 or Mo2Ti2C328,37.

For Mo concentrations larger than x = 2, the most stable model in each case is formed by the full substitution of the VI sites and a random arrangement of Mo in the VII sites, see models I in Fig. S3. The less stable models are formed by the random deposition of Mo in VI and VII sites or by alternating Mo and V layers along the c direction.

We also investigated the lattice parameter evolution vs. Mo content (see Fig. 2). The upper and lower panels correspond to a and c lattice parameters. The a parameter expands from 2.90 Å to 3.09 Å (6.5%), from x = 0 to x = 4, which fulfills Vegard's law. On the other hand, c parameter achieves its maximum expansion (2.49%, 23.14 Å) at x = 2.5. After that, the cell parameter slightly contracts, reaching 23.07 Å for x = 4, which violates Vegard's law. This fact can be attributed to the large electronegativity difference between Mo and V and the presence of covalent bonds, as previously reported for different compounds63,64. According to the calculations, the MoxV4-xAlC3 MAX alloy follows Vegard's law until x = 2.5, demonstrating that our theoretical results agree with the experimental findings of Pinto et al.44.

Cell parameters of the MoxV4-xAlC3 MAX alloy as a function of the Mo content. The upper and lower panels are for cell parameters a and c, respectively.

The changes in the different bonds present in the alloy are investigated. The results are listed in Table 2. Notice that when increasing the Mo content in the structure, the bonds suffer an expansion, which is an expected result since Mo has a large atomic radius. The VI-C is expanded from 1.98 Å for the V4AlC3 to 2.00 Å for the Mo1.5V2.5AlC3 MAX alloy. About VII-C at Mo concentrations lower than x = 2, the bond distance remains practically unaltered since Mo only occupies VI sites. However, for higher concentrations (x > 2), the bond distance increases considerably due to the occupation of the VII sites. Moreover, Mo occupying VI sites (MoI) provides large bond distances compared to VI-C. At concentrations higher than x = 2, Mo occupies VII sites (MoII). MoII generates larger bond distances than VII, which rises as the Mo content goes from 2.13 Å in Mo2.5V1.5AlC3 to 2.19 in Mo4AlC3.

We employed the DFE formalism described in the methodology section to investigate the thermodynamic stability of the different alloys. We only considered the most stable configuration for each Mo content according to Table 1. We vary the chemical potential from V-rich to V-poor conditions and from Mo-rich to Mo-moderate conditions to evaluate the thermodynamic stability of the MAX alloys. We do not consider Mo-poor conditions since the pristine MAX phase is the only stable in that chemical potential region. Figure S4 shows the 3D plot, where each plane represents a different alloy. According to our formalism, the most stable models depict the lowest energy values. Although the 3D representation helps distinguish the stable models, it is difficult to differentiate the chemical potential regions where the models are stable. We project the 3D plot into a 2D phase diagram with well-defined growth limits to solve this problem. Figure 3 displays the phase diagram for the MoxV4-xAlC3 MAX solid solution. At V-rich and Mo-moderate conditions, the pristine V4AlC3 compound is the most stable model (purple surface). Notice that the Mo doping is carried out in the region from V-moderate to V-poor conditions and from Mo-moderate to Mo-rich conditions. Our calculations show four stable and different MoxV4-xAlC3 (with x = 0.5,1, 1.5, and 2) alloys. Also, it is noticed that as the μV trend to V-poor and the μMo moves to Mo-rich conditions, the Mo content increases until reaching the double-ordered alloy V2Mo2AlC3. The atomistic models of the most stable models are shown in Fig. 4. Our DFE analysis agrees with the experimental results reported by Pinto et al.44. However, they successfully obtained the Mo2.7V1.3AlC3 alloy disagrees with our findings. A possible explanation is that the alloy mentioned above can be obtained due to border effects -not considered in our study- in which VII sites are not in an FCC stacking, generating an energy gain when Mo occupies those sites.

Corresponding phase diagram of the MAX MoxV4-xAlC3 alloy.

Atomistic models for the five stable MAX alloys according to the DFE formalism. We show the models as the Mo content increases from left to right.

In this section, we perform a Bader charge analysis in combination with ELF line profiles to investigate the nature of the bonding interactions in the stable systems. Note from the line profiles that ELF tends to zero as it reaches the atoms’ core due to using pseudopotentials. Bader analysis of the pristine V4AlC3 MAX shows that the VII atoms donate 0.25e to each of its six C neighbors. VI atoms donate 0.28e to their neighboring C atoms; this change evidence a stronger interaction in VI-C than in VII-C. This effect is seen in the ELF line profile (see Fig. 1c), where it is noticed that both bonds exhibit a mainly ionic behavior. Also, it is notorious for a major population of electrons along the VI-C bond. Moreover, the Al atoms accept 0.17e from the V nearest neighbor.

In the case of the stable MoxV4-xAlC3 alloys, where Mo substitutes the VI atoms, we notice that Mo donates 0.23e to each of its bonds formed with C. This behavior supposes that Mo donates fewer electrons in comparison with V. ELF line profiles explain this effect showing a bond nature change from ionic to covalent, see Fig. S5. Despite this, the VII-C interactions do not change. VII remains donating 0.25e to each of its six C neighbors (Fig. S5). However, unlike pristine V4AlC3, Al donates 0.55e to neighboring Mo atoms in the case of the alloys.

In this subsection, we analyzed the DOS of the most stable alloys. The corresponding DOS for MoxV4-xAlC3 with x = 0.5, 1, 1.5, and 2 are depicted in Fig. S6, SI. In all cases, the energy reference is the Fermi level. Positive and negative values along the DOS axis corresponds with spin up and down, respectively. As in the pristine MAX (see Fig. 1), the alloys exhibit a metallic behavior with non-magnetic characteristics. The main contribution to the DOS around the Fermi level comes from the V-3d orbitals, followed by the Mo-4d orbitals, which increase their contribution to the DOS as Mo content increases.

Once we studied the stability and bond nature of the MoxV4-xAlC3 alloys, we focused on investigating the exfoliation energy of the so-called MXenes. As a first approximation, we do not consider the presence of functional groups on the surface to isolate the Mo content effect in the exfoliation process. We only consider the extreme cases, x = 0 and x = 2. NEB calculations have been performed to investigate the minimum energy pathway (MEP), see Fig. 5a. The energy reference, Initial State (IS), is the V-terminated (Mo-terminated) (0001) surface, and the Final State (FS) occurs when the MXene is far enough to interact with the surface. The MXene exfoliation is an endothermic process; for the V4AlC3 is 0.37 eV/Å2, while for the ordered alloy, Mo2V2AlC3, the energy is 0.35 eV/Å2. Results demonstrate that Mo reduces the exfoliation energy, an effect explained through Bader charge analysis and ELF in the previous subsection.

(a) minimum energy pathway for the exfoliation of a monolayer of V4C3 (black points) and Mo2V2C3 (red points) MXenes, (b) phase diagram for the thermodynamic stability of the different MoxV4-xC3 MXenes.

We also investigated the thermodynamic stability of the MXenes in a similar way to the MAX compounds. Their corresponding phase diagram is displayed in Fig. 5b. As we can see, the alloys are stable at V-poor and Mo-rich conditions, while the pristine V4C3 MXene is stable at V-rich conditions in the entire region from Mo-rich to Mo-moderate conditions. Similarly, to the MAX case, in the MXenes, the Mo content increases as reaching V-poor and Mo-rich conditions until obtaining the double-ordered Mo2V2C3 MXene alloy. The atomistic models of the stable MXenes are depicted in Fig. 6.

Atomic models of the stable MXenes according to Fig. 5b.

Through a systematic ab-initio assessment, we investigated the thermodynamic stability of the MXene precursor MoxV4-xAlC3 in the 0 ≤ x ≤ 4 range. Mo incorporation generates an increase in a, while c expands until x = 2.5. Above such concentration, a slight contraction in c appears. Mo incorporates in a random, however, it achieves an order in the out-of-plane Mo2V2AlC3. From all the considered concentrations, we found five thermodynamically stable compounds (V4AlC3, Mo0.5V3.5AlC3, MoV3AlC3, Mo1.5V2.5AlC3, and Mo2V2AlC3) at different growth conditions. Electron Localization Function shows that V-C bonds are ionic while Mo-C covalent. Finally, we evaluated the exfoliation energy in the limiting stable cases (V4AlC3 and Mo2V2AlC3), since the changes in the bonding type induced by the Mo incorporation, the exfoliation of the Mo2V2AlC3 is more favorable. Finally, our results evidence that five MXenes can be obtained from their counterpart MAX phase alloys.

The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.

Sokol, M., Natu, V., Kota, S. & Barsoum, M. W. On the chemical diversity of the MAX Phases. Trends Chem. 1, 210. https://doi.org/10.1016/j.trechm.2019.02.016 (2019).

Article CAS Google Scholar

Zhang, J., Liu, B., Wang, J. Y. & Zhou, Y. C. Low-temperature instability of Ti2SnC: A combined transmission electron microscopy, differential scanning calorimetry, and x-ray diffraction investigations. J. Mater. Res. 24, 39. https://doi.org/10.1557/JMR.2009.0012 (2009).

Article ADS CAS Google Scholar

Lin, Z., Zhuo, M., Zhou, Y., Li, M. & Wang, J. Microstructures and theoretical bulk modulus of layered ternary tantalum aluminum carbides. J. Am. Ceram. Soc. 89, 3765. https://doi.org/10.1111/j.1551-2916.2006.01303.x (2006).

Article CAS Google Scholar

Zheng, L. et al. (Ti0.5Nb0.5)5AlC4: A new-layered compound belonging to MAX phases. J. Am. Ceram. Soc. 93, 3068. https://doi.org/10.1111/j.1551-2916.2010.04056.x (2010).

Article CAS Google Scholar

Zhou, Y., Meng, F. & Zhang, J. New MAX-phase compounds in the V-Cr–Al–C system. J. Am. Ceram. Soc. 91, 1357. https://doi.org/10.1111/j.1551-2916.2008.02279.x (2008).

Article CAS Google Scholar

Deysher, G. et al. Synthesis of Mo4VAlC4 MAX phase and two-dimensional Mo4VC4 MXene with five atomic layers of transition metals. ACS Nano 14, 204. https://doi.org/10.1021/acsnano.9b07708 (2020).

Article CAS PubMed Google Scholar

Wang, X. H. & Zhou, Y. C. Layered machinable and electrically conductive Ti2AlC and Ti3AlC2 ceramics: A review. J. Mater Sci. Technol. 26, 385. https://doi.org/10.1016/S1005-0302(10)60064-3 (2010).

Article Google Scholar

Jin, S., Su, T., Hu, Q. & Zhou, A. Thermal conductivity and electrical transport properties of double-A-layer MAX phase Mo2Ga2C. Mater. Res. Lett. 8, 158. https://doi.org/10.1080/21663831.2020.1724204 (2020).

Article CAS Google Scholar

Wei, H. et al. Effects of Ti2SnC on the mechanical properties and tribological properties of copper/graphite composites. Ceram. Int. 48, 36853. https://doi.org/10.1016/j.ceramint.2022.08.250 (2022).

Article CAS Google Scholar

Barsoum, M. W. MAX Phases: Properties of Machinable Ternary Carbides and Nitrides (Wiley-VCH Verlag GmbH & Co. KGaA, 2013). https://doi.org/10.1002/9783527654581.

Book Google Scholar

Yang, A., Duan, Y., Bao, L., Peng, M. & Shen, Li. Elastic properties, tensile strength, damage tolerance, electronic and thermal properties of TM3AlC2 (TM = Ti, Zr and Hf) MAX phases: A first-principles study. Vacuum 206, 111497. https://doi.org/10.1016/j.vacuum.2022.111497 (2022).

Article ADS CAS Google Scholar

Barsoum, M. W. & Radovic, M. Elastic and mechanical properties of the MAX phases. Annu. Rev. Mater. Res. 41, 195. https://doi.org/10.1146/annurev-matsci-062910-100448 (2011).

Article ADS CAS Google Scholar

Li, S., Li, H., Zhou, Y. & Zhai, H. Mechanism for abnormal thermal shock behavior of Cr2AlC. J. Eur. Ceram. Soc. 34, 1083. https://doi.org/10.1016/j.jeurceramsoc.2013.12.003 (2014).

Article CAS Google Scholar

Chirica, I. M. et al. Applications of MAX phases and MXenes as catalysts. J. Mater. Chem. A 9, 19589. https://doi.org/10.1039/D1TA04097A (2021).

Article CAS Google Scholar

Wesley, H. K. et al. The Ti3AlC2 MAX phase as an efficient catalyst for oxidative dehydrogenation of n-Butane. Chem. Int. Ed. 57, 1485. https://doi.org/10.1002/anie.201702196 (2018).

Article CAS Google Scholar

Huang, Q. et al. Irradiation resistance of MAX phases Ti3SiC2 and Ti3AlC2: Characterization and comparison. J. Nucl. Mater. 465, 640. https://doi.org/10.1016/j.jnucmat.2015.06.056 (2015).

Article ADS CAS Google Scholar

Wang, C. et al. Ion-irradiation-induced structural evolution in Ti4AlN3. Scr. Mater. 133, 19. https://doi.org/10.1016/j.scriptamat.2017.02.014 (2017).

Article CAS Google Scholar

Gonzalez-Julian, J., Mauer, G., Sebold, D., Mack, D. E. & Vassen, R. Cr2AlC MAX phase as bond coat for thermal barrier coatings: Processing, testing under thermal gradient loading, and future challenges. J. Am. Ceram. Soc. 103, 2362. https://doi.org/10.1111/jace.16935 (2020).

Article CAS Google Scholar

Tallman, D. J., Anasori, B. & Barsoum, M. W. A critical review of the oxidation of Ti2AlC, Ti3AlC2 and Cr2AlC in air. Mater. Res. Lett. 1, 115. https://doi.org/10.1080/21663831.2013.806364 (2013).

Article CAS Google Scholar

Basu, S., Obando, N., Gowdy, A., Karaman, I. & Radovic, M. Long-term oxidation of Ti2AlC in air and water vapor at 1000–1300 °C temperature range. J. Electrochem. Soc. 159, C90. https://doi.org/10.1149/2.jes120017 (2012).

Article CAS Google Scholar

Haftani, M., Heydari, M. S., Baharvandi, H. R. & Ehsani, N. Studying the oxidation of Ti2AlC MAX phase in atmosphere: A review. Int. J. Refract. Hard Met. 61, 51. https://doi.org/10.1016/j.ijrmhm.2016.07.006 (2016).

Article CAS Google Scholar

Gogotsi, Y. & Anasori, B. The rise of MXenes. ACS Nano 13, 8491. https://doi.org/10.1021/acsnano.9b06394 (2019).

Article CAS PubMed Google Scholar

Naguib, M. et al. Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2. Adv. Mater. 23, 4248. https://doi.org/10.1002/adma.201102306 (2011).

Article CAS PubMed Google Scholar

Tahir, R., Zahra, S. A., Naeem, U., Akinwande, D. & Rizwan, S. First observation on emergence of strong room-temperature ferroelectricity and multiferroicity in 2D-Ti3C2Tx free-standing MXene film. RSC Adv. 12, 24571. https://doi.org/10.1039/D2RA04428E (2022).

Article ADS CAS PubMed PubMed Central Google Scholar

Zahra, S. A., Hakim, M. W., Mansoor, M. A. & Rizwan, S. Two-dimensional double transition metal carbides as superior bifunctional electrocatalysts for overall water splitting. Electrochim. Acta 434, 141257. https://doi.org/10.1016/j.electacta.2022.141257 (2022).

Article CAS Google Scholar

Fatima, S., Bin, X., Mohammad, M. A., Akinwande, D. & Rizwan, S. Graphene and MXene based free-standing carbon memristors for flexible 2D memory applications. Adv. Electron. Mater. 8, 2100549. https://doi.org/10.1002/aelm.202100549 (2022).

Article CAS Google Scholar

Syamsai, R. et al. Double transition metal MXene (TixTa4−xC3) 2D materials as anodes for Li-ion batteries. Sci. Rep. 11, 688. https://doi.org/10.1038/s41598-020-79991-8 (2021).

Article ADS CAS PubMed PubMed Central Google Scholar

Maldonado-Lopez, D. et al. Atomic-scale understanding of Li storage processes in the Ti4C3 and chemically ordered Ti2Ta2C3 MXenes: A theoretical and experimental assessment. ACS Appl. Energy Mater. 5, 1801. https://doi.org/10.1021/acsaem.1c03239 (2022).

Article CAS Google Scholar

Zahra, S. A., Ceesay, E. & Rizwan, S. Zirconia-decorated V2CTx MXene electrodes for supercapacitors. J. Energy Storage 55, 105721. https://doi.org/10.1016/j.est.2022.105721 (2022).

Article Google Scholar

Fatima, M. et al. Experimental and computational analysis of MnO2@V2C-MXene for enhanced energy storage. Nanomaterials 11, 1707. https://doi.org/10.3390/nano11071707 (2021).

Article CAS PubMed PubMed Central Google Scholar

Zaheer, A. et al. Nickel-adsorbed two-dimensional Nb2C MXene for enhanced energy storage applications. RSC Adv. 12, 4624. https://doi.org/10.1039/D2RA00014H (2022).

Article ADS CAS PubMed PubMed Central Google Scholar

Liu, Z. et al. Crystal structure and formation mechanism of (Cr2/3Ti1/3)3AlC2 MAX phase. Acta Mater. 73, 186. https://doi.org/10.1016/j.actamat.2014.04.006 (2014).

Article ADS CAS Google Scholar

Hamm, C. M., Bocarsly, J. D., Seward, G., Kramm, U. I. & Birkel, C. S. Non-conventional synthesis and magnetic properties of MAX phases (Cr/Mn)2AlC and (Cr/Fe)2AlC. J. Mater. Chem. C 5, 5700. https://doi.org/10.1039/C7TC00112F (2017).

Article CAS Google Scholar

Salikhov, R. et al. Magnetic properties of nanolaminated (Mo0.5Mn0.5)2GaC MAX phase. J. Appl. Phys. 121, 163904. https://doi.org/10.1063/1.4982197 (2017).

Article ADS CAS Google Scholar

Tao, Q. et al. Two-dimensional Mo1.33C MXene with divacancy ordering prepared from parent 3D laminate with in-plane chemical ordering. Nat. Commun. 8, 14949. https://doi.org/10.1038/ncomms14949 (2017).

Article ADS PubMed PubMed Central Google Scholar

Thore, A. & Rosen, J. An investigation of the in-plane chemically ordered atomic laminates (Mo2/3Sc1/3)2AlC and (Mo2/3Y1/3)2AlC from first principles. Phys. Chem. Chem. Phys. 19, 21595. https://doi.org/10.1039/C7CP03228E (2017).

Article CAS PubMed Google Scholar

Anasori, B. et al. Experimental and theoretical characterization of ordered MAX phases Mo2TiAlC2 and Mo2Ti2AlC3. J. Appl. Phys. 118, 094304. https://doi.org/10.1063/1.4929640 (2015).

Article ADS CAS Google Scholar

Anasori, B. et al. Mo2TiAlC2: A new ordered layered ternary carbide. Scr. Mater. 101, 5. https://doi.org/10.1016/j.scriptamat.2014.12.024 (2015).

Article CAS Google Scholar

Anasori, B. et al. Two-dimensional, ordered, double transition metals carbides (MXenes). ACS Nano 9, 9507. https://doi.org/10.1021/acsnano.5b03591 (2015).

Article CAS PubMed Google Scholar

Griseri, M. et al. Ta-based 413 and 211 MAX phase solid solutions with Hf and Nb. J. Eur. Ceram. Soc. 40, 1829. https://doi.org/10.1016/j.jeurceramsoc.2019.12.052 (2020).

Article CAS Google Scholar

Cedillos-Barraza, O. et al. Investigating the highest melting temperature materials: A laser melting study of the TaC-HfC system. Sci. Rep. 6, 37962. https://doi.org/10.1038/srep37962 (2016).

Article ADS CAS PubMed PubMed Central Google Scholar

Hong, Q.-J. & van de Walle, A. Prediction of the material with highest known melting point from ab initio molecular dynamics calculations. Phys. Rev. B 92, 020104. https://doi.org/10.1103/PhysRevB.92.020104 (2015).

Article ADS CAS Google Scholar

Qu, L. et al. Synthesis, crystal structure, microstructure and mechanical properties of (Ti1-xZrx)3SiC2 MAX phase solid solutions. Ceram. Int. 45, 1400. https://doi.org/10.1016/j.ceramint.2018.10.030 (2019).

Article CAS Google Scholar

Pinto, D. et al. Synthesis and electrochemical properties of 2D molybdenum vanadium carbides—Solid solution MXenes. J. Mater. Chem. A 8, 8957. https://doi.org/10.1039/D0TA01798A (2020).

Article CAS Google Scholar

Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558. https://doi.org/10.1103/PhysRevB.47.558 (1993).

Article ADS CAS Google Scholar

Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251. https://doi.org/10.1103/PhysRevB.49.14251 (1994).

Article ADS CAS Google Scholar

Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mat. Sci. 6, 15–50. https://doi.org/10.1016/0927-0256(96)00008-0 (1996).

Article CAS Google Scholar

Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169. https://doi.org/10.1103/PhysRevB.54.11169 (1996).

Article ADS CAS Google Scholar

Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865. https://doi.org/10.1103/PhysRevLett.77.3865 (1996).

Article ADS CAS PubMed Google Scholar

Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953. https://doi.org/10.1103/PhysRevB.50.17953 (1994).

Article ADS CAS Google Scholar

Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758. https://doi.org/10.1103/PhysRevB.59.1758 (1999).

Article ADS CAS Google Scholar

Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104. https://doi.org/10.1063/1.3382344 (2010).

Article ADS CAS PubMed Google Scholar

Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456. https://doi.org/10.1002/jcc.21759 (2011).

Article CAS PubMed Google Scholar

Monkhorst, H. & Pack, J. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188. https://doi.org/10.1103/PhysRevB.13.5188 (1976).

Article ADS MathSciNet Google Scholar

Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901. https://doi.org/10.1063/1.1329672 (2000).

Article ADS CAS Google Scholar

Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978. https://doi.org/10.1063/1.1323224 (2000).

Article ADS CAS Google Scholar

Qian, G. X., Martin, R. M. & Chadi, D. J. First-principles study of the atomic reconstructions and energies of Ga- and As-stabilized GaAs(100) surfaces. Phys. Rev. B 38, 7649. https://doi.org/10.1103/PhysRevB.38.7649 (1988).

Article ADS CAS Google Scholar

Moreno, J. C. H., Ponce-Pérez, R., Cocoletzi, G. H. & Takeuchi, N. Antiferromagnetic coupling in the initial stages of the MnN epitaxial growth on the CrN (0 0 1) surface. Appl. Surf. Sci. 573, 151451. https://doi.org/10.1016/j.apsusc.2021.151451 (2022).

Article CAS Google Scholar

Ponce-Perez, R., Moreno-Armenta, M. G. & Guerrero-Sánchez, J. Selective incorporation of Fe and Co into the Ni2MnGa (001) surfaces: A DFT analysis. Surf. Interfaces 34, 102367. https://doi.org/10.1016/j.surfin.2022.102367 (2022).

Article CAS Google Scholar

Moreno Hernández, J. C., Ponce-Pérez, R., Cocoletzi, G. H., Hoat, D. M. & Takeuchi, N. Tuning the half-metallicity in reconstructed CrN (111) surfaces. Surf. Interfaces 35, 102420. https://doi.org/10.1016/j.surfin.2022.102420 (2022).

Article CAS Google Scholar

Hu, C. et al. Crystal structure of V4AlC3: A new layered ternary carbide. J. Am. Ceram. Soc. 91, 636. https://doi.org/10.1111/j.1551-2916.2007.02136.x (2008).

Article CAS Google Scholar

Yu, W. et al. Solid solution effects in the Ti2Al(CxNy) MAX phases: Synthesis, microstructure, electronic structure and transport properties. Acta Mater. 80, 421. https://doi.org/10.1016/j.actamat.2014.07.064 (2014).

Article CAS Google Scholar

Wang, G., Zhou, J. & Sun, Z. First principles investigation on anomalous lattice shrinkage of W alloyed rock salt GeTe. J. Phys. Chem. Solids 137, 109220. https://doi.org/10.1016/j.jpcs.2019.109220 (2020).

Article CAS Google Scholar

Khan, M. A., Gueddim, A., Bouarissa, N., Algarni, H. & Ziani, H. Band parameters for Zn1−xMoxTe studied by means of spin-polarized first-principles calculations. J. Comput. Electron. 19, 38. https://doi.org/10.1007/s10825-019-01430-3 (2020).

Article CAS Google Scholar

Download references

We thank DGAPA-UNAM projects IN101523, IA100822, IN110820, and IG200320 for partial financial support. Calculations were performed in the DGCTIC-UNAM Supercomputing Center projects, LANCAD-UNAM-DGTIC-422, LANCAD-UNAM-DGTIC-368 and LANCAD-UNAM-DGTIC-150. JGS acknowledges LNS-BUAP project 202201042N and THUBAT KAAL IPICYT supercomputing center project TKII-JGSA001 for their computational resources. We thank E. Murillo and Aldo Rodriguez-Guerrero for their technical support and valuable discussions.

Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Km. 107, Apdo. Postal 14. Carretera Tijuana-Ensenada, Ensenada, Baja California, México

Ma. Guadalupe Moreno-Armenta, J. Guerrero-Sánchez, S. J. Gutiérrez-Ojeda & R. Ponce-Pérez

Facultad de Ciencias Físico Matemáticas, Universidad Autónoma de Nuevo León, 66451, San Nicolas de los Garza, Nuevo León, México

H. N. Fernández-Escamilla

Institute of Theoretical and Applied Research, Duy Tan University, Ha Noi, 100000, Vietnam

D. M. Hoat

Faculty of Natural Sciences, Duy Tan University, Da Nang, 550000, Vietnam

D. M. Hoat

You can also search for this author in PubMed Google Scholar

Credit author statement M.G.M.-A.: Formal analysis, resources, writing review & editing, funding acquisition, supervision. J.G.-S.: conceptualization, methodology, resources, writing review & editing, funding acquisition. S.J.G.-O.: Formal analysis, writing review & editing. H.N.F.-E.: Formal analysis, writing review & editing. D.M.H.: Formal analysis, writing review & editing. R.P.-P.: conceptualization, methodology, formal analysis, investigation, writing original draft, visualization. All authors reviewed the manuscript.

Correspondence to Ma. Guadalupe Moreno-Armenta or R. Ponce-Pérez.

The authors declare no competing interests.

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

Moreno-Armenta, M.G., Guerrero-Sánchez, J., Gutiérrez-Ojeda, S.J. et al. Theoretical investigation of the MXene precursors MoxV4-xAlC3 (0 ≤ x ≤ 4). Sci Rep 13, 3271 (2023). https://doi.org/10.1038/s41598-023-30443-z

Download citation

Received: 22 November 2022

Accepted: 23 February 2023

Published: 25 February 2023

DOI: https://doi.org/10.1038/s41598-023-30443-z

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.