The relaxation dynamics of water in hygroscopic molecular solids is probed by broadband dielectric spectroscopy in the temperature range from 200 to 450 K. Evidence is found for three types of dynamic processes. The intermediate process is common to all probed materials and is associated with the reorientation of bound water molecules that are attached directly onto organic molecules and counterions. A faster process is observed in rhodamine chloride and fullerol, which is the dynamic signature of water in higher hydration layers, either at grain boundaries (rhodamine) or in interstitial clusters (fullerol). All these processes are observed near room temperature and exhibit nonmonotonic temperature dependence and decreasing spectral strength upon heating. In fullerol a third, ultraslow relaxation is observed at high temperature, which may be due to the reorientation of water–fullerol complexes or to the diffusion of water vapor through intermolecular voids.

Impedance spectroscopy is employed to probe the frequency-dependent conductivity and dielectric response of the C60O24Na24 fulleride. The conduction properties of this organic material match the so-called universal behavior of the ac conductivity in disordered media [Dyre, J. C.; Schroder, T. B. Rev. Mod. Phys. 2000, 72, 873–892]. In the whole temperature range studied, electrical conduction is due to intermolecular hopping processes of electronic charge carriers, characterized by an effective activation energy ranging between 0.7 eV at room temperature and 0.9 eV at 475 K. A single dielectric loss feature is observed, associated with the hopping of charge carriers surrounded by a polarization cloud. The polarizability of the material is mainly due to the distortion of the ionic O–Na bonds of the fullerene derivative, which are tight enough that no ionic contribution to the conductivity is observed up to the highest temperature probed (550 K).

Graphene oxide (GO) is well known as an excellent amphiphilic material due to its oxygen-containing functional groups and its chemical tunability. By intercalation chemistry, organo-modified GO containing sulfonilic terminal groups were prepared and used as nanoadditive in Nafion polymer for the creation of hybrid exfoliated composites. The incorporation of hydrophilic 2D platelike layers in the Nafion membranes is expected to induce advantages in terms of thermal stability and mechanical and barrier properties (limitation of the methanol crossover by increased tortuosity and obstruction effect), although it may negatively affect the proton conductivity. In this work, we show how different preparation methods of the nanocomposites influence morphology, transport properties, and barrier effect to methanol. The hybrid membranes are characterized by powder X-ray diffraction and microscopies (SEM, TEM, and AFM). Water and methanol transport properties inside the nanocomposites are investigated by NMR spectroscopy (diffusivity and relaxation times), unveiling a reduction of the methanol diffusion and, nevertheless, an increase in the proton mobility and water retention at high temperatures. Finally, the electrochemical properties are investigated by direct methanol fuel cell (DMFC) tests, showing a significant reduction of the ohmic losses at high temperatures, extending in this way the operating range of a DMFC.

Impedance spectroscopy is employed to probe the impact of water on the dc conductivity and ac dielectric response of the polycrystalline C 60 (ONa) 24 fulleride, both in its bulk-hydrate form, stable only below 370 K, and in the pure form, obtained by heating to high temperature. Exposure of the pure material to ambient air results in the condensation of water vapor on the crystallites' surface, which in turn leads to an enhancement of the room-temperature conductivity by four orders of magnitude due to charge transport through the hydration layer. Electrical conduction in the hydrate between 320 and 380 K is dominated by a non-equilibrium contribution associated with the structural water, which leads to a value of the dc conductivity that is higher than that of the pure material by almost two decades at 360 K. Both conductivity enhancements are most likely due to a proton exchange mechanism. All impedance spectra exhibit, in the radiofrequency range, a dielectric loss feature related to the accumulation of free charges at grain boundaries, whose strength is strongly affected by the presence of hydration water.

CO2 hydrogenation toward methane, a reaction of high environmental and sustainable energy importance, was investigated at 200–600 °C and H2/CO2 = 4/1, over Rh nanoparticles dispersed on supports with different oxygen storage capacity characteristics (γ-Al2O3, alumina-ceria-zirconia, and ceria-zirconia). The effects of the support OSC and Rh particle size on reaction behavior under both integral and differential conditions were investigated, to elucidate the combined role of these crucial catalyst design parameters on methanation efficiency. A volcano-type variation of methanation turnover frequency was found in respect to support OSC; Rh/ACZ, with intermediate OSC, was the optimal catalyst. The structure sensitivity of the reaction was found to be a combined function of support OSC and Rh particle size: For Rh/γ-Al2O3 (lack of OSC) methanation was strongly favored on small particles—the opposite for Rh/CZ (high OSC). The findings are promising for rational design and optimization of CO2 methanation catalysts by tailoring the aforementioned characteristics.