2D rare-earth metal carbides (MXenes) are attractive due to their novel electronic and magnetic properties and their potential as scalable 2D magnets. In this study, we used density functional theory with the Hubbard U correction to characterize the structure, termination, and magnetism in an out-of-plane ordered rare-earth containing M 3 C 2 T x MXene, Mo 2 NdC 2 T 2 (T = O or OH). We investigated the effect of the U parameter on the stability and magnetism of two possible termination sites: the hollow sites aligned with the inner Nd atoms (Nd-hollow sites) and those aligned with the closest C atoms (C-hollow sites). We found that increasing U Mo stabilized the Nd hollow sites, which minimized electrostatic repulsion between C and O atoms. Using U Mo = 3.0 eV and U Nd = 5.6 eV, obtained via the linear response method, we found that the energetically preferred termination site was C-hollow in Mo 2 NdC 2 O 2 and Nd-hollow in Mo 2 NdC 2 (OH) 2 . Regardless of termination and the Hubbard U value, we found Mo 2 NdC 2 O 2 and Mo 2 NdC 2 (OH) 2 to be magnetic. The C-hollow termination resulted in ferromagnetic states for all Hubbard U tested with no magnetic moment in Mo. In the case of Nd-hollow, Mo became magnetic for U Mo ≥ 4 eV. The difference of Mo magnetism in Nd-hollow and C-hollow was explained by crystal field splitting of the Mo d orbital caused by a distorted ligand.
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Synthesis of layered vs planar Mo 2 C: role of Mo diffusion
Abstract Chemical vapor deposition growth of metal carbides is of great interest as this method provides large area growth of MXenes. This growth is mainly done using a melted diffusion based process; however, different morphologies in growth process is not well understood. In this work, we report deterministic synthesis of layered (non-uniform c -axis growth) and planar (uniform c -axis growth) of molybdenum carbide (Mo 2 C) using a diffusion-mediated growth. Mo-diffusion limited growth mechanism is proposed where the competition between Mo and C adatoms determines the morphology of grown crystals. Difference in thickness of catalyst at the edge and center lead to enhanced Mo diffusion which plays a vital role in determining the structure of Mo 2 C. The layered structures exhibit an expansion in the lattice confirmed by the presence of strain. Density functional theory shows consistent presence of strain which is dependent upon Mo diffusion during growth. This work demonstrates the importance of precise control of diffusion through the catalyst in determining the structure of Mo 2 C and contributes to broader understanding of metal diffusion in growth of MXenes.
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- Award ID(s):
- 1929356
- NSF-PAR ID:
- 10338518
- Date Published:
- Journal Name:
- 2D Materials
- Volume:
- 9
- Issue:
- 1
- ISSN:
- 2053-1583
- Page Range / eLocation ID:
- 015039
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Two-dimensional graphene-like materials, namely MXenes, have been proposed as potential materials for various applications. In this work, the reactivity and selectivity of four MXenes ( i.e. M 2 C (M = Ti, V, Nb, Mo)) and their oxygen-functionalized forms ( i.e. O-MXenes or M 2 CO 2 ) toward gas molecules were investigated by using the plane wave-based Density Functional Theory (DFT) calculations. Small gas molecules, which are commonly found in flue gas streams, are considered herein. Our results demonstrated that MXenes are very reactive. Chemisorption is a predominant process for gas adsorption on MXenes. Simultaneously dissociative adsorption can be observed in most cases. The high reactivity of their non-functionalized surface is attractive for catalytic applications. In contrast, their reactivity is reduced, but the selectivity is improved upon oxygen functionalization. Mo 2 CO 2 and V 2 CO 2 present good selectivity toward NO molecules, while Nb 2 CO 2 and Ti 2 CO 2 show good selectivity toward NH 3 . The electronic charge properties explain the nature of the substrates and also interactions between them and the adsorbed gases. Our results indicated that O-MXenes are potential materials for gas-separation/capture, -storage, -sensing, etc. Furthermore, their structural stability and SO 2 -tolerant nature are attractive properties for using them in a wide range of applications. Our finding provides good information to narrow down the choices of materials to be tested in future experimental work.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1088/2053-1583/ac43fa
