Direct force measurements between negatively charged silica particles in the presence of a like-charged strong polyelectrolyte were carried out with an atomic force microscope. The force profiles can be quantitatively interpreted as a superposition of depletion and double-layer forces. The depletion forces are modeled with a damped oscillatory profile, while the double-layer forces with the mean-field Poisson-Boltzmann theory for a strongly asymmetric electrolyte, whereby an effective valence must be assigned to the polyelectrolyte. This effective valence is substantially smaller than the bare valence due to ion condensation effects. The unusual aspect of the electrical double layer in these systems is the exclusion of the like-charged polyelectrolyte from the vicinity of the surface, leading to a strongly nonexponential diffuse ionic layer that is dominated by counterions and has a well-defined thickness. As the oscillatory depletion force sets in right after this layer, this condition can be used to predict the phase of the oscillatory depletion force.
A broad family of the nowadays studied low-dimensional systems, including 2D materials, demonstrate many fascinating properties, which however depend on the atomic composition as well as on the system dimensionality. Therefore, the studies of the electronic correlation effects in the new 2D materials is of paramount importance for the understanding of their transport, optical and catalytic properties. Here, by means of electron spectroscopy methods in combination with density functional theory calculations we investigate the electronic structure of a new layered van der Waals $$\hbox {FePX}_3$$ FePX 3 (X: S, Se) materials. Using systematic resonant photoelectron spectroscopy studies we observed strong resonant behavior for the peaks associated with the $$3d^{n-1}$$ 3 d n - 1 final state at low binding energies for these materials. Such observations clearly assign $$\hbox {FePX}_3$$ FePX 3 to the class of Mott–Hubbard type insulators for which the top of the valence band is formed by the hybrid Fe-S/Se electronic states. These observations are important for the deep understanding of this new class of materials and draw perspectives for their further applications in different application areas, like (opto)spintronics and catalysis.
Complexation between poly(acrylate) (PA) and poly(allylammonium) (PAH) macroions at pH = 7.0 was studied by means of electrokinetics, microcalorimetry, and DLS. At low polyelectrolyte concentrations and no electrolyte present strong overcharging of primary nanocomplexes occurred. In contrast, the increase in polyelectrolyte concentration led to flocculation taking place near the equivalence. The nanocomplex charge reversal was also achieved in the high polymer concentration regime by the abrupt instead of stepwise titrant addition. The procedure was successfully used in the case of several other polyion pairs. The presence of electrolyte affected the PAH–PA interpolyelectrolyte neutralization considerably, leading to ion-specific aggregation and extrinsic charge compensation. The complexation energetics was weakly influenced by ionic conditions. To the best of our knowledge, the reported results are the first direct evidence for primary complex overcharging. Their rationalization explains why interpolyelectrolyte neutralization in solution and at surfaces usually results in formation of neutral and charged products, respectively.
A broad family of the nowadays studied low-dimensional systems, including 2D materials, demonstrate many fascinating properties, which however depend on the atomic composition as well as on the system dimensionality. Therefore, the studies of the electronic correlation effects in the new 2D materials is of paramount importance for the understanding of their transport, optical and catalytic properties. Here, by means of electron spectroscopy methods in combination with density functional theory calculations we investigate the electronic structure of a new layered van der Waals FePX 3 (X: S, Se) materials. Using systematic resonant photoelectron spectroscopy studies we observed strong resonant behavior for the peaks associated with the 3d n−1 final state at low binding energies for these materials. Such observations clearly assign FePX 3 to the class of Mott-Hubbard type insulators for which the top of the valence band is formed by the hybrid Fe-S/Se electronic states. These observations are important for the deep understanding of this new class of materials and draw perspectives for their further applications in different application areas, like (opto)spintronics and catalysis.
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