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We report the intercalation of polyacrylonitrile nanoparticles in Ti3C2Tx MXene layers through simple sonication. The use of polyacrylonitrile, which was synthesized via radical polymerization, offered dual benefits: (1) It increased the interlayer spacing of MXene, thereby exposing more surface area and enhancing ion transport channels during charge and discharge cycles, and (2) Integrating MXene with polyacrylonitrile enables the creation of a composite with conductive properties, following percolation principle. X-ray diffraction analysis showed an increase in the c-lattice parameter, indicative of the interlayer spacing, from 22.31 Å for the pristine MXene to 37.73 Å for the MXene−polyacrylonitrile composite. The intercalated polyacrylonitrile nanoparticles facilitated the delamination by weakening the interlayer interactions, especially during sonication. Electrochemical assessments revealed significant improvement in the properties of the MXene−polyacrylonitrile composite compared to the pristine MXene. The assembled asymmetric device achieved a good specific capacitance of 32.1 F/g, an energy density of 11.42 W h/kg, and 82.2% capacitance retention after 10,000 cycles, highlighting the practical potential of the MXene−polyacrylonitrile composite.
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Step‐by‐Step Guide for Synthesis and Delamination of Ti 3 C 2 T x MXene
To advance the MXene field, it is crucial to optimize each step of the synthesis process and create a detailed, systematic guide for synthesizing high-quality MXene that can be consistently reproduced. In this study, a detailed guide is provided for an optimized synthesis of titanium carbide (Ti3C2Tx) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric-Ti3AlC2 MAX phase and delamination of the etched multilayered Ti3C2Tx MXene using lithium chloride at 65 °C for 1 h with argon bubbling. The effect of different synthesis variables is investigated, including the stoichiometry of the mixed powders to synthesize Ti3AlC2, pre-etch impurity removal conditions, selective etching, storage, and drying of MXene multilayer powder, and the subsequent delamination conditions. The synthesis yield and the MXene film electrical conductivity are used as the two parameters to evaluate the MXene quality. Also the MXenes are characterized with scanning electron microscopy, x-ray diffraction, atomic force microscopy, and ellipsometry. The Ti3C2Tx film made via the optimized method shows electrical conductivity as high as ≈21,000 S/cm with a synthesis yield of up to 38 %. A detailed protocol is also provided for the Ti3C2Tx MXene synthesis as the supporting information for this study.
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- Award ID(s):
- 1950672
- PAR ID:
- 10654622
- Publisher / Repository:
- Wiley-VCH GmbH
- Date Published:
- Journal Name:
- Small Methods
- Volume:
- 7
- Issue:
- 8
- ISSN:
- 2366-9608
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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MXenes are a newer class of 2D materials, possess with desirable properties such as large specific surface area, conductivity, and hydrophilicity, making them attractive for various environmental applications, including remediation and as membranes for water treatment. Until recently, the practical implementation of MXenes was hindered by their instability in water, although improved synthesis procedures have largely addressed this issue. Consequently, it is now important to assess the stability of MXenes in engineered environments relevant to drinking water and membrane operation (e.g. backwashing). In this study, Ti3C2Tx MXenes were found to remain stable upon exposure to an aqueous environment saturated with oxygen and to UVC and UVA light at circumneutral pH, but were transformed upon exposure to Fe(III) chloride and free chlorine. The chlorination reaction kinetics are 1st order with respect to Ti3C2Tx and free chlorine concentration, with a rate constant that increased at pH ≤ 7.5, implicating HOCl as the reactive species. We propose that MXene reactions with HOCl occur by an electrophilic attack of Cl+, forming TiO2 and degrading the MXene. AFM data shows that transformations are initiated at the edges of the MXene sheets and localized areas on the MXene, suggesting that the initial sites for Cl+ attack are defect sites and/or uncoordinated Ti atoms. During the initial stages of the oxidative degradation, the sheet-like structure of colloidal MXenes is preserved, although prolonged chlorine exposure leads to three-dimensional crystalline (anatase) TiO2 formation. The degradation of MXenes during chlorinationThis contrasts with the inertness of nanoscale TiC, highlighting the need to devise surface modification processes that will allow MXenes to resist the oxidative conditions associated with membrane regeneration/backwashing.more » « less
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With varying hydrofluoric acid (HF) concentrations under three etching conditions, we presented a comparative study of the effects of both the ordered and randomly ternary mixed terminated Ti3C2Tx surfaces with a wide variation of O/OH/F stoichiometry on the thermodynamic stability and electronic properties. Regardless of the HF concentration, an OH-rich surface is found to be thermodynamically stable and the electrical conductivity of Ti3C2Tx is substantially affected by the OH concentration. The charge density difference and electron localization function demonstrated a significant electron localization at the hydroxyl group on the O/OH/F mixed terminated surface, which could yield a locally induced dipole on the surface that renders favorable reaction sites on the functionalized surface. In addition, a large tunability in the work function (ΔΦ ∼ 3.5 eV) is predicted for Ti3C2Tx. These findings provide a pathway for strategically tuning the electronic and structural properties of Ti3C2 MXenes etched with HF.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/smtd.202300030
