Journal article
Effect of Base/Nucleophile Treatment on Interlayer Ion Intercalation, Surface Terminations, and Osmotic Swelling of Ti3C2Tz MXene Multilayers
Chemistry of materials, v 34(2), pp 678-693
25 Jan 2022
Abstract
The first MXene discovered, Ti3C2Tz, was synthesized by etching aluminum, Al, from the nanolaminated MAX phase, Ti3AlC2, using hydrofluoric acid, HF. To delaminate the resulting MXene multilayers, MLs, it was necessary to increase the interlayer spacing, by first treating them with relatively large organic cations such as tetrabutylammonium hydroxide, TBAOH, dimethyl sulfoxide, DMSO, etc. When etched with a combination of LiF and HCl on the other hand, the Li cations spontaneously intercalated and no extra delamination step was needed. Herein, we attempt to understand why some molecules intercalate into the HF-etched MXene, while others do not. We find that treating HF-etched Ti3C2Tz MLs with a base, like NaOH, renders them ion exchangeable. This base treatment was found to reduce the -F terminations on the MXene surfaces, which most likely weakens the interlayer hydrogen bonding and therefore allows for ion exchange and concomitant hydration. We exploit this nucleophilic dehalogenation to functionalize the Ti3C2Tz surfaces using several different nucleophiles like sodium stearate, lithium ethoxide, and diisopropyl xanthogen polysulfide. We also demonstrate the effect of interlayer ions and other functional terminations on the electrochemical performance of Ti3C2Tz in sodium ion and lithium sulfur batteries. Finally, we find that the interlayer spacing between MXene sheets derived using LiF + HCl increases dramatically when exposed to low-concentration salt solutions; this was attributed to osmotic swelling. This phenomenon was earlier observed in clays but is shown for the first time in the case of MXenes.
Metrics
Details
- Title
- Effect of Base/Nucleophile Treatment on Interlayer Ion Intercalation, Surface Terminations, and Osmotic Swelling of Ti3C2Tz MXene Multilayers
- Creators
- Varun Natu - Drexel UniversityRahul Pai - Drexel UniversityOlivia Wilson - Drexel UniversityEdward Gadasu - Drexel UniversityHussein Badr - Drexel UniversityAvishek Karmakar - Drexel UniversityAndrew J. D. Magenau - Drexel UniversityVibha Kalra - Drexel UniversityMichel W. Barsoum - Drexel University
- Publication Details
- Chemistry of materials, v 34(2), pp 678-693
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 16
- Grant note
- DMR-1740795; PFI-TT 1919177 / NSF; National Science Foundation (NSF)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Materials Science and Engineering; Chemical and Biological Engineering
- Web of Science ID
- WOS:000740504500001
- Scopus ID
- 2-s2.0-85122790577
- Other Identifier
- 991019168336004721