First-principles exploration of Sc- and Y-based MXenes with halogen terminations
Source abstract
Abstract
Abstract Transition metal carbides and nitrides (MXenes) have been extensively studied owing to their compositional diversity and tunable properties, with Y- and Sc-based MXenes predicted to exhibit semiconductor behavior. While top-down synthesis of Sc- and Y-based MXenes is hindered by the lack of suitable precursors, existing crystalline stacks of multilayer Sc/Y carbides offer new strategies for achieving these MXenes. In this study, we theoretically investigated Sc- and Y-based MXenes with halogen terminations (F, Cl, Br, and I), examining their lattice structures, electronic properties, and potential applications. Multilayer structures of halogen-terminated Sc and Y MXenes were confirmed by first-principles calculations, in which the exfoliation of two-dimensional multilayers with Cl, Br, and I terminations was found to be achievable, whereas F-terminated stacks are expected to remain in multilayer structures. Semiconducting carbides, regardless of dimensionality, show promise for photocatalytic water splitting with tunable catalytic performance under different pH conditions.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: MXene and MAX Phase Materials · 2D Materials and Applications · Advanced Photocatalysis Techniques
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (56)
Show source-provided references
1. Naguib, M. et al. Two-dimensional nanocrystals produced by exfoliation of Ti3 AlC2. Adv. Mater. 23, 4248–4253 (2011).10.1002/adma.201102306 ↗
2. VahidMohammadi, A., Rosen, J. & Gogotsi, Y. The world of two-dimensional carbides and nitrides (MXenes). Science 372, eabf1581 (2021).10.1126/science.abf1581 ↗
3. Naguib, M. et al. MXene: a promising transition metal carbide anode for lithium-ion batteries. Electrochem. Commun. 16, 61–64 (2012).10.1016/j.elecom.2012.01.002 ↗
4. Naguib, M. et al. New two-dimensional niobium and vanadium carbides as promising materials for Li-ion batteries. J. Am. Chem. Soc. 135, 15966–15969 (2013).10.1021/ja405735d ↗
5. Hantanasirisakul, K. et al. Fabrication of Ti3C2T MXene Transparent Thin Films with Tunable Optoelectronic Properties. Adv. Electron. Mater. 2, 1600050 (2016).10.1002/aelm.201600050 ↗
6. Kamysbayev, V. et al. Covalent surface modifications and superconductivity of two-dimensional metal carbide MXenes. Science 369, 979–983 (2020).10.1126/science.aba8311 ↗
7. Li, Z. et al. Direct methane activation by atomically thin platinum nanolayers on two-dimensional metal carbides. Nat. Catal. 4, 882–891 (2021).10.1038/s41929-021-00686-y ↗
8. Dahlqvist, M., Barsoum, M. W. & Rosen, J. MAX phases—past, present, and future. Mater. Today 72, 1–24 (2024).10.1016/j.mattod.2023.11.010 ↗
9. Halim, J. et al. Transparent conductive two-dimensional titanium carbide epitaxial thin films. Chem. Mater. 26, 2374–2381 (2014).10.1021/cm500641a ↗
10. Ghidiu, M., Lukatskaya, M. R., Zhao, M.-Q., Gogotsi, Y. & Barsoum, M. W. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature 516, 78–81 (2014).10.1038/nature13970 ↗
11. Li, M. et al. Element replacement approach by reaction with Lewis acidic molten salts to synthesize nanolaminated MAX phases and MXenes. J. Am. Chem. Soc. 141, 4730–4737 (2019).10.1021/jacs.9b00574 ↗
12. Rems, E. et al. Computationally guided synthesis of MXenes by dry selective extraction. Adv. Mater. 35, 2305200 (2023).10.1002/adma.202305200 ↗
13. Niu, K., Chi, L., Rosen, J. & Björk, J. C–H activation of light alkanes on MXenes predicted by hydrogen affinity. Phys. Chem. Chem. Phys. 22, 18622–18639 (2020).10.1039/D0CP02471F ↗
14. Niu, K., Chi, L., Rosen, J. & Björk, J. Structure-activity correlation of Ti2CT2 MXenes for C-H activation. J. Phys. 33, 235201 (2021).
15. Wang, F. et al. Advances in molten-salt-assisted synthesis of 2D MXenes and their applications in electrochemical energy storage and conversion. Chem. Eng. J. 470, 144185 (2023).10.1016/j.cej.2023.144185 ↗
16. Li, Y. et al. A general Lewis acidic etching route for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte. Nat. Mater. 19, 894–899 (2020).10.1038/s41563-020-0657-0 ↗
17. Li, M. et al. Halogenated Ti3C2 MXenes with Electrochemically Active Terminals for High-Performance Zinc Ion Batteries. ACS Nano 15, 1077–1085 (2021).10.1021/acsnano.0c07972 ↗
18. Ding, H. et al. Chemical scissor–mediated structural editing of layered transition metal carbides. Science 379, 1130–1135 (2023).10.1126/science.add5901 ↗
19. Zhou, C. et al. Hybrid organic–inorganic two-dimensional metal carbide MXenes with amido- and imido-terminated surfaces. Nat. Chem. 15, 1–8 (2023).10.1038/s41557-023-01288-w ↗
20. Zhou, J., Dahlqvist, M., Björk, J. & Rosen, J. Atomic scale design of mxenes and their parent materials─from theoretical and experimental perspectives. Chem. Rev. 123, 13291–13322 (2023).10.1021/acs.chemrev.3c00241 ↗
21. Liu, J.-H., Kan, X., Amin, B., Gan, L.-Y. & Zhao, Y. Theoretical exploration of the potential applications of Sc-based MXenes. Phys. Chem. Chem. Phys. 19, 32253–32261 (2017).10.1039/C7CP06224A ↗
22. Mostafaei, A. & Abbasnejad, M. Computational studies on the structural, electronic and optical properties of M2CT2 (M = Y, Sc and T = F, Cl) MXene monolayer. J. Alloy. Compd. 857, 157982 (2021).10.1016/j.jallcom.2020.157982 ↗
23. Li, Y. et al. Regulating the electronic structure of MAX phases based on rare earth element Sc to enhance electromagnetic wave absorption. ACS Nano 18, 10019–10030 (2024).10.1021/acsnano.3c11585 ↗
24. Meshkian, R. et al. Theoretical stability and materials synthesis of a chemically ordered MAX phase, Mo2ScAlC2, and its two-dimensional derivate Mo2ScC2 MXene. Acta Mater. 125, 476–480 (2017).10.1016/j.actamat.2016.12.008 ↗
25. Wang, D. et al. Direct synthesis and chemical vapor deposition of 2D carbide and nitride MXenes. Science 379, 1242–1247 (2023).10.1126/science.add9204 ↗
26. Hwu, S. J., Ziebarth, R. P., Von Winbush, S., Ford, J. E. & Corbett, J. D. Synthesis and structure of double-metal-layered scandium, yttrium, and zirconium chloride carbides and nitrides, M2Cl2C and M2Cl2N. Inorg. Chem. 25, 283–287 (1986).10.1021/ic00223a011 ↗
27. Druffel, D. L. et al. Synthesis and Electronic Structure of a 3D Crystalline Stack of MXene-Like Sheets. Chem. Mater. 31, 9788–9796 (2019).10.1021/acs.chemmater.9b03722 ↗
28. Maeda, K. et al. Visible-light-induced photocatalytic activity of stacked MXene sheets of Y2CF2. J. Phys. Chem. C 124, 14640–14645 (2020).10.1021/acs.jpcc.0c03072 ↗
29. Kempt, R. et al. Stacking polymorphism in PtSe2 drastically affects its electromechanical properties. Adv. Sci. 9, 2201272 (2022).10.1002/advs.202201272 ↗
30. Zhang, T. et al. Delamination of chlorine-terminated mxene produced using molten salt etching. Chem. Mater. 36, 1998–2006 (2024).10.1021/acs.chemmater.3c02872 ↗
31. Zhou, L., Zhang, Y., Zhuo, Z., Neukirch, A. J. & Tretiak, S. Interlayer-decoupled Sc-based mxene with high carrier mobility and strong light-harvesting ability. J. Phys. Chem. Lett. 9, 6915–6920 (2018).10.1021/acs.jpclett.8b03077 ↗
32. Zeng, Q. et al. Two-dimensional Sc2CCl2/XSe2(X = Mo, Pt) van der Waals heterojunctions: promising photocatalytic hydrogen evolution materials. ChemPhysChem 25, e202400304 (2024).10.1002/cphc.202400304 ↗
33. Björk, J. & Rosen, J. Functionalizing MXenes by tailoring surface terminations in different chemical environments. Chem. Mater. 33, 9108–9118 (2021).10.1021/acs.chemmater.1c01264 ↗
34. Hamada, I. van der Waals density functional made accurate. Phys. Rev. B 89, 121103 (2014).10.1103/PhysRevB.89.121103 ↗
35. Han, S. S. et al. Horizontal-to-vertical transition of 2D layer orientation in low-temperature chemical vapor deposition-grown PtSe2 and its influences on electrical properties and device applications. ACS Appl. Mater. Interfaces 11, 13598–13607 (2019).10.1021/acsami.9b01078 ↗
36. Duong, D. L., Yun, S. J. & Lee, Y. H. van der Waals layered materials: opportunities and challenges. ACS Nano 11, 11803–11830 (2017).10.1021/acsnano.7b07436 ↗
37. Björkman, T., Gulans, A., Krasheninnikov, A. V. & Nieminen, R. M. van der Waals bonding in layered compounds from advanced density-functional first-principles calculations. Phys. Rev. Lett. 108, 235502 (2012).10.1103/PhysRevLett.108.235502 ↗
38. Mounet, N. et al. Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds. Nat. Nanotech. 13, 246–252 (2018).10.1038/s41565-017-0035-5 ↗
39. Heyd, J., Scuseria, G. E. & Ernzerhof, M. Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]. J. Chem. Phys. 124, 219906 (2006).10.1063/1.2204597 ↗
40. Xie, Y. & Kent, P. Hybrid density functional study of structural and electronic properties of functionalized Tin+1Xn (X = C, N) monolayers. Phys. Rev. B 87, 235441 (2013).10.1103/PhysRevB.87.235441 ↗
41. Sun, R., Yang, C.-L., Wang, M.-S. & Ma, X.-G. Two-dimensional Sc2CCl2/SiS2 van der Waals heterostructure with high solar power conversion efficiency. Appl. Surf. Sci. 591, 153232 (2022).10.1016/j.apsusc.2022.153232 ↗
42. Shah, N., Wang, X. & Tian, J. Recent advances in MXenes: a promising 2D material for photocatalysis. Mater. Chem. Front. 7, 4184–4201 (2023).10.1039/D3QM00216K ↗
43. Li, L. & Shen, G. MXene based flexible photodetectors: progress, challenges, and opportunities. Mater. Horiz. 10, 5457–5473 (2023).10.1039/D3MH01362F ↗
44. Gan, L.-Y. & Schwingenschlögl, U. Two-dimensional square ternary Cu2MX4 (M = Mo, W; X = S, Se) monolayers and nanoribbons predicted from density functional theory. Phys. Rev. B 89, 125423 (2014).10.1103/PhysRevB.89.125423 ↗
45. Chakrapani, V. et al. Charge transfer equilibria between diamond and an aqueous oxygen electrochemical redox couple. Science 318, 1424–1430 (2007).10.1126/science.1148841 ↗
46. Valdés, Á, Qu, Z.-W., Kroes, G.-J., Rossmeisl, J. & Nørskov, J. K. Oxidation and photo-oxidation of water on TiO2 surface. J. Phys. Chem. C 112, 9872–9879 (2008).10.1021/jp711929d ↗
47. Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
48. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).10.1103/PhysRevB.50.17953 ↗
49. Heyd, J., Scuseria, G. E. & Ernzerhof, M. Hybrid functionals based on a screened Coulomb potential. J. Chem. Phys. 118, 8207–8215 (2003).10.1063/1.1564060 ↗
50. Maintz, S., Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J. Comput. Chem. 34, 2557–2567 (2013).10.1002/jcc.23424 ↗
51. Maintz, S., Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. LOBSTER: A tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chem. 37, 1030–1035 (2016).10.1002/jcc.24300 ↗
52. Deringer, V. L., Tchougreeff, A. L. & Dronskowski, R. Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. J. Phys. Chem. A 115, 5461–5466 (2011).10.1021/jp202489s ↗
53. Togo, A. First-principles phonon calculations with phonopy and Phono3py. J. Phys. Soc. Jpn 92, 012001 (2023).10.7566/JPSJ.92.012001 ↗
54. Togo, A. & Tanaka, I. First principles phonon calculations in materials science. Scr. Mater. 108, 1–5 (2015).10.1016/j.scriptamat.2015.07.021 ↗
55. Born, M., Huang, K., Born, M. & Huang, K. Dynamical Theory of Crystal Lattices. (Oxford University Press, Oxford, New York, 1998).
56. Eriksson, F., Fransson, E. & Erhart, P. The hiphive package for the extraction of high-order force constants by machine learning. Adv. Theory Simul. 2, 1800184 (2019).10.1002/adts.201800184 ↗