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.
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Green synthesis of reduced Ti 3 C 2 T x MXene nanosheets with enhanced conductivity, oxidation stability, and SERS activity
Transition metal carbides (MXenes) are an emerging family of highly conductive two-dimensional materials with additional functional properties introduced by surface terminations. Further modification of the surface terminations makes MXenes even more appealing for practical applications. Herein, we report a facile and environmentally benign synthesis of reduced Ti 3 C 2 T x MXene (r-Ti 3 C 2 T x ) via a simple treatment with l -ascorbic acid at room temperature. r-Ti 3 C 2 T x shows a six-fold increase in electrical conductivity, from 471 ± 49 for regular Ti 3 C 2 T x to 2819 ± 306 S m −1 for the reduced version. Additionally, we show an enhanced oxidation stability of r-Ti 3 C 2 T x as compared to regular Ti 3 C 2 T x . An examination of the surface-enhanced Raman scattering (SERS) activity reveals that the SERS enhancement factor of r-Ti 3 C 2 T x is an order of magnitude higher than that of regular Ti 3 C 2 T x . The improved SERS activity of r-Ti 3 C 2 T x is attributed to the charge transfer interaction between the MXene surface and probe molecules, re-enforced by an increased electronic density of states (DOS) at the Fermi level of r-Ti 3 C 2 T x . The findings of this study suggest that reduced MXene could be a superior choice over regular MXene, especially for the applications that employ high electronic conductivity, such as electrode materials for batteries and supercapacitors, photodetectors, and SERS-based sensors.
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- PAR ID:
- 10176273
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 8
- Issue:
- 14
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 4722 to 4731
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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