Two-dimensional
(2D) transition metal carbides and nitrides (MXenes)
have shown outstanding performances in electrochemical energy storage
and many other applications. Delamination of MXene flakes in water
produces colloidal solutions that are used to manufacture all kinds
of products (thin films, coatings, and electrodes, etc.). However,
the stability of MXene colloidal solutions, which is of critical importance
to their application, remains largely unexplored. Here we report on
the degradation of delaminated-Ti3C2T
x
colloidal solutions (T represents the surface functionalities)
and outline protocols to improve their stability. Ti3C2T
x
MXene solutions in open vials
degraded by 42%, 85%, and 100% after 5, 10, and 15 days, respectively,
leading to the formation of cloudy-white colloidal solutionss containing
primarily anatase (TiO2). On the other hand, the solution
could be well-preserved when Ti3C2T
x
MXene colloidal solutionss were stored in hermetic
Ar-filled bottles at 5 °C, because dissolved oxygen, the main
oxidant of the MXene flakes, was eliminated. Under such a recipe,
the time constant of the solution was dramatically increased. We have
found that the degradation starts at the edges and its kinetics follows
the single-exponential decay quite well. Moreover, we performed size
selection of the MXene solution via a cascade technique and showed
that the degradation process is also size-dependent, with the small
flakes being the least stable. Furthermore, a dependence between the
degradation time constants and the flake size allows us to determine
the size of the nanosheets in situ from UV–vis
spectra and vice versa. Finally, the proposed method
of storing the MXene colloidal solution in Ar-filled vials was applied
to Ti2CT
x
to improve its stability
and time constant, demonstrating the validity of this protocol in
improving the lifetime of different MXene solutions.
Nanoscale optical band gap variations in epitaxial thin films of two different spinel ferrites, i.e., NiFe2O4 (NFO) and CoFe2O4 (CFO), have been investigated by spatially resolved high resolution electron energy loss spectroscopy. Experimentally, both NFO and CFO show indirect/direct band gaps around 1.52 eV/2.74 and 2.3 eV, and 1.3 eV/2.31 eV, respectively, for the ideal inverse spinel configuration with considerable standard deviation in the band gap values for CFO due to various levels of deviation from the ideal inverse spinel structure. Direct probing of the regions in both the systems with tetrahedral A site cation vacancy, which is distinct from the ideal inverse spinel configuration, shows significantly smaller band gap values. The experimental results are supported by the density functional theory based modified Becke-Johnson exchange correlation potential calculated band gap values for the different cation configurations.
Layer specific direct measurement of optical band gaps of two important van der Waals compounds, MoS2 and ReS2, is performed at nanoscale by high resolution electron energy loss spectroscopy. For monolayer MoS2, the twin excitons (1.8 and 1.95 eV) originating at the K point of the Brillouin zone are observed. An indirect band gap of 1.27 eV is obtained from the multilayer regions. Indirect to direct band gap crossover is observed which is consistent with the previously reported strong photoluminescence from the monolayer MoS2. For ReS2, the band gap is direct, and a value of 1.52 and 1.42 eV is obtained for the monolayer and multilayer, respectively. The energy loss function is dominated by features due to high density of states at both the valence and conduction band edges, and the difference in analyzing band gap with respect to ZnO is highlighted. Crystalline 1T ReS2 forms two dimensional chains like superstructure due to the clustering between four Re atoms. The results demonstrate the power of HREELS technique as a nanoscale optical absorption spectroscopy tool.
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