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.

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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.

Electroosmotic flow (EOF), a consequence of an imposed electric field onto an electrolyte solution in the tangential direction of a charged surface, has emerged as an important phenomenon in electrokinetic transport at the micro/nanoscale. Because of their ability to efficiently pump liquids in miniaturized systems without incorporating any mechanical parts, electroosmotic methods for fluid pumping have been adopted in versatile applications—from biotechnology to environmental science. To understand the electrokinetic pumping mechanism, it is crucial to identify the role of an ionically polarized layer, the so‐called electrical double layer (EDL), which forms in the vicinity of a charged solid–liquid interface, as well as the characteristic length scale of the conducting media. Therefore, in this tutorial review, we summarize the development of electrical double layer models from a historical point of view to elucidate the interplay and configuration of water molecules and ions in the vicinity of a solid–liquid interface. Moreover, we discuss the physicochemical phenomena owing to the interaction of electrical double layer when the characteristic length of the conducting media is decreased from the microscale to the nanoscale. Finally, we highlight the pioneering studies and the most recent works on electro osmotic flow devoted to both theoretical and experimental aspects.

The control of biomolecule translocation through nanopores is important in nanopore protein detection. Improvement in current nanopore molecule control is desired to enhance capture rates, extend translocation times, and ensure the effective detection of various proteins in the same solutions. We present a method that simultaneously resolves these issues through the use of a gate-modulated conical nanopore coupled with solutions of varying salt concentration. Simulation results show that the presence of an induced reverse electroosmotic flow (IREOF) results in inlet flows from the two ends of the nanopore centerline entering into the nanopore in opposite directions, which simultaneously elevates the capture rate and immobilizes the protein in the nanopore, thus enabling steady current blockage measurements for a range of proteins. In addition, it is shown that proteins with different size/charge ratios can be trapped by a gate modulation intensified flow field at a similar location in the nanopore in the same solution conditions.

The simultaneous concentration gradient focusing and separation of proteins in a silica nanofluidic channel of various geometries is investigated experimentally and theoretically. Previous modelling of a similar device [Inglis et al., Angew. Chem. Int. Ed., 2011, 50, 7546] assumed a uniform velocity profile along the length of the nanochannel. Using detailed numerical analysis incorporating charge regulation and viscoelectric effects, we show that in reality the varying axial electric field and varying electric double layer thickness caused by the concentration gradient, induce a highly non-uniform velocity profile, fundamentally altering the protein trapping mechanism: the direction of the local electroosmotic flow reverses and two local vortices are formed near the centreline of the nanochannel at the low salt concentration end, enhancing trapping efficiency. Simulation results for yellow/red fluorescent protein R-PE concentration enhancement, peak focusing position and peak focusing width are in good agreement with experimental measurements, validating the model. The predicted separation of yellow/red (R-PE) from green (Dyl-Strep) fluorescent proteins mimics that from a previous experiment [Inglis et al., Angew. Chem. Int. Ed., 2011, 50, 7546] conducted in a slightly different geometry. The results will inform the design of new class of matrix-free particle focusing and separation devices.

Single entity electrochemistry (SEE) has emerged as a promising method for precise measurement and fundamental understanding of the heterogeneity of single entities. Herein, we propose the dual responsive SEE sensing of the silver nanoparticles (AgNPs) collisions through a wireless nanopore electrode (WNE). Given the high temporal resolution and low background noise features, the Faradaic and capacitive currents provide the AgNPs’ collision response. The electron transfer between the AgNPs and the electrode surface is identified under a bipolar electrochemical mechanism. Compared to the ultramicroelectrode, multistep oxidation of 30 nm AgNPs is observed due to the decreased interaction of the nanoparticles to the electrode. Moreover, the nanoconfinement of WNE plays a vital role in the repeated capturing of nanoparticles from the nontunneling region into the tunneling region until a complete oxidation. As a comparison, the collision of 5 nm AgNPs with higher interaction at the electrode surface shows great decrease in the multistep events. Thus, we propose a nanoconfined interaction based SEE method which could be used for simultaneously capturing the Faradaic and capacitive response. The nanoconfined interaction based SEE method holds great promise in the better understanding of heterogeneity of single particles.