The thermal dependence of salinity-gradient-driven energy conversion by reverse electrodialysis using a mesoporous silica thin film with pores ca. 2-3 nm in diameter was studied in a temperature range of 293-333 K. As the temperature increases, the surface charge density of mesopores increases owing to an increase in the zeta potential of the pore walls, which in turn increases the concentration of counter-ions in the electrical double layer. The ion mobility also increases with increasing temperature owing to a decrease in the liquid viscosity. As a result, the temperature increase improves the ion conductance of mesopores both in the surface-charge-governed regime at low ion concentrations and in the bulk regime at high ion concentrations. However, further increases in temperature induce bubble nucleation. In particular, in highly concentrated salt solutions, hydrophobic patches appear on the pore surfaces because of the salting-out effect and mask the surface charge. The weakened polarity in mesopores allows more co-ions to enter them, decreasing the potential difference across the film, resulting in a serious deterioration of the energy conversion efficiency. The thermal dependence of the performance characteristics of mesoporous-silica-based nanofluidic devices was also evaluated.

Electrokinetic transport behavior in nanochannels is different to that in larger sized channels. Specifically, molecular dynamics (MD) simulations in nanochannels have demonstrated two little understood phenomena which are not observed in microchannels, being : (i) the decrease of average electroosmotic mobility at high surface charge density, and (ii) the decrease of channel conductance at high salt concentrations, as the surface charge is increased. However, current electric double layer models do not capture these results. In this study we provide evidence that this inconsistency primarily arises from the neglect of the viscoelectric effect (being the increase of local viscosity near charged surfaces due to water molecule orientation) in conventional continuum models. It is shown that predictions of electroosmotic mobility in a slit nanochannel, derived from a viscoelectricmodified continuum model, are in quantitative agreement with previous MD simulation results. Furthermore, viscoelectric effects are found to dominate over ion steric and dielectric saturation effects in both electroosmotic and ion transport processes. Finally, we indicate that mechanisms of the previous MD-observed phenomena can be well-explained by the viscoelectric theory.

Nanofluidic energy harvesting systems have attracted interest in the field of battery application, particularly for miniaturized electrical devices, because they possess excellent energy conversion capability for their size. In this study, a mesoporous silica (MPS)-based nanofluidic energy harvesting system was fabricated and selective ion transport in mesopores as a function of the salt gradient was investigated. Aqueous solutions with three different kinds of monovalent electrolytes-KCl, NaCl, and LiCl-with different diffusion coefficients (D) were considered. The highest power density was 3.90 W m for KCl, followed by 2.39 W m for NaCl and 1.29 W m for LiCl. Furthermore, the dependency of power density on the type of cation employed indicates that the harvested energy increases as the cation mobility increases, particularly at high concentrations. This cation-specific dependency suggests that the maximum power density increases by increasing the diffusion coefficient ratio of cations to anions, making this ratio a critical parameter in enhancing the performance of nanofluidic energy harvesting systems with extremely small pores ranging from 2 to 3 nm.

The adsorption−desorption isotherms and relaxation curves of water in chromium terephthalate metal−organic frameworks (MOFs), MIL-101, were measured by the gravimetric method at 298 K and 1 atm. The obtained isotherms were compared to those obtained by the volumetric method, which showed good agreement. The measured isotherms exhibited three-step and two-step curves during adsorption and desorption, respectively. The hysteresis between adsorption and desorption isotherms was not pronounced, and the difference in relative humidity between the adsorption and desorption isotherms was 0.05−0.10 at identical adsorbed mass. Regarding the water adsorption relaxation curves, when the relative humidity was varied stepwise from 0.40 to 0.47 and the water supply rate was small, the relaxation curves could be fitted to two straight lines, indicating that, initially, the middle cages filled with water, followed by the large cages at a different adsorption rate. When the relative humidity was changed stepwise from 0.40 to 0.90 and the water supply rate was large, the relaxation curves could be fitted to a single straight line until the equilibrium state, and the relaxation time was about 40 s. The kinetics of water transport inside MIL-101 is strongly dependent on its unique pore structure and hydrophilicity−hydrophobicity spatial distribution.

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Mesoporous silica SBA-16 thin films with highly ordered 3D cubic structures were synthesized on a Si substrate via the dip-coating method. After these films were filled with KCl aqueous solutions, the ionic current passing through the mesopores was measured by applying dc electric fields. At low ion concentrations, the measured I-V curves were nonlinear and the current increased exponentially with respect to voltage. As the ion concentration increased, the I-V curve approached linear behavior. The nonlinear behavior of I-V curves can be reasonably attributed to the electric potential barrier created in nanopores.

Mesoporous silica SBA-16 thin films with highly ordered 3D cubic structures were synthesized by an evaporation-induced self-assembly method, using an F127 triblock copolymer as the structure-directing agent via dip coating, to investigate the proton transport of aqueous solutions confined in mesopores. Using electrochemical measurements of ionic current under DC electric fields, we elucidated proton transport phenomena through mesopores of SBA-16 thin films. At low concentrations, ranging from 10(-7) to 10(-5) M, the I-V curves of KCl and HCl aqueous solutions were nonlinear. However, at 10(-4) and 10(-3) M, while I-V curves of KCl aqueous solutions displayed nonlinear behavior, those of HCl aqueous solutions were almost linear. The linear behavior can be attributed to a decrease in the electric potential barrier owing to a reduction in the surface charge density, which is caused by the protonation of silanol groups on the inner surface of mesopores. At high concentrations, ranging from 10(-2) to 1 M, the I-V curves of KCl and HCl aqueous solutions were almost linear because the effect of surface charge of mesopores on ion transport was marginal.

Two-dimensional hexagonal mesoporous silica thin films of SBA-15 were synthesized on Si substrates via dip-coating using an evaporation-induced self-assembly process. The effect of the withdrawal speed on the thicknesses, one-dimensional pore alignments, and two-dimensional hexagonal pore arrays of the films was elucidated. Detailed analyses of FE-SEM and TEM images and XRD and XRR patterns of the synthesized thin films clarified that the pore sizes, interplanar spacings, and film thicknesses depend on the withdrawal speed. Furthermore, the same films were synthesized on Si substrates with microtrenches. The local flow of coating solutions around microtrenches affects the pore direction as well as the film thickness. In order to form well-ordered mesoporous silica thin films with large surface areas, it is important to control the synthetic conditions such as the local flow of the coating solutions as well as the physicochemical properties of the silica precursor solutions or template molecules.