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Abstract MXenes, a family of 2D transition‐metal carbides and nitrides, have excellent electrical conductivity and unique optical properties. However, MXenes oxidize in ambient conditions, which is accelerated upon heating. Intercalation of water also causes hydrolysis accelerating oxidation. Developing new tools to readily characterize MXenes’ thermal stability can enable deeper insights into their structure–property relationships. Here, in situ spectroscopic ellipsometry (SE) is employed to characterize the optical properties of three types of MXenes (Ti3C2Tx, Mo2TiC2Tx, and Ti2CTx) with varied composition and atomistic structures to investigate their thermal degradation upon heating under ambient environment. It is demonstrated that changes in MXene extinction and optical conductivity in the visible and near‐IR regions correlate well with the amount of intercalated water and hydroxyl termination groups and the degree of oxidation, measured using thermogravimetric analysis. Among the three MXenes, Ti3C2Txand Ti2CTx, respectively, have the highest and lowest thermal stability, indicating the role of transition‐metal type, synthesis route, and the number of atomic layers in MXene flakes. These findings demonstrate the utility of SE as a powerful in situ technique for rapid structure–property relationship studies paving the way for the further design, fabrication, and property optimization of novel MXene materials.
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Imaging and simulation of surface plasmon polaritons on layered 2D MXenes
Two-dimensional (2D) transition metal carbides and nitrides, commonly known as MXenes, are a class of 2D materials with high free carrier densities, making them highly attractive candidates for plasmonic 2D materials. In this study, we use multiphoton photoemission electron microscopy (nP-PEEM) to directly image the plasmonic near fields of multilayers of the prototypical MXene, Ti3C2Tx, with mixed surface terminations (Tx = F, O, and OH). Photon-energy dependentnP-PEEM reveals a dispersive surface plasmon polariton between 1.4 and 1.9 electron volts on MXene flakes thicker than 30 nanometers and waveguide modes above 1.9 electron volts. Combining experiments with finite-difference time-domain simulations, we reveal the emergence of a visible surface plasmon polariton in MXenes, opening avenues for exploration of polaritonic phenomena in MXenes in the visible portion of the electromagnetic spectrum.
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- PAR ID:
- 10590258
- Publisher / Repository:
- American Association for the Advancement of Science
- Date Published:
- Journal Name:
- Science Advances
- Volume:
- 11
- Issue:
- 12
- ISSN:
- 2375-2548
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Ti3C2Tx(MXenes) are novel 2D nanomaterials with exceptional electrical conductivity. Their surfaces are covered with functional groups that may significantly affect material properties such as hydrophobicity, electrical conductivity, and oxidation resistance. The role of these terminations in high-temperature ceramic systems with regard to phase and microstructural evolution has not been investigated. In this study, Ti3C2Tx-SiOC 2D nanocomposites were fabricated with -F and -OH terminated MXene to evaluate the role of surface terminations in silane coupling and phase formation during the polymer-to-ceramic transformation. X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) identified self-etching mechanisms caused by F-terminated Ti3C2Txand revealed that the F surface terminations were retained in the MXene structure until evolution at ~ 550 °C. Evolved F reacted with Si–H bonds in the transforming ceramic matrix, causing additional mass loss and volumetric deformation. LiOH alkalization was shown to suppress the self-etching phenomenon through the substitution of F groups with OH on the nanosheet surface. Furthermore, F terminations were determined to only engage in hydrogen bonding with silane molecules as opposed to covalent linkages with OH terminations, which accelerated silane removal and Ti3C2Txdegradation. The study provides a fundamental understanding of the nature and behavior of MXene surface terminations in the context of high-temperature ceramic nanocomposite fabrication.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1126/sciadv.ads3689
