Single Mesopores with High Surface Charges as Ultrahigh Performance Osmotic Power Generators.

Numerous studies on osmotic power generators with nanoscale pores are conducted. However, their performance output is limited because of the finite osmotic current and conductance from such tiny pores. Here, a proof-of-concept study demonstrating that the rectified mesopore (sub-micrometer-scale pore) with high surface charges can be applied in osmotic energy conversion is reported. A single conical mesopore of ≈405 nm in tip diameter, which can reach an osmotic conductance as high as 0.284 µS (corresponding to a current of 27.5 nA and voltage of 97 mV), enables a record-high power of 667 pW under a 1000-fold salinity gradient, more than doubling all of the state-of-the-art single-pore osmotic power generators reported. This work extends the knowledge of osmotic energy with solid-state pores from nanoscale to mesoscale and opens up a promising avenue toward ultrahigh performance osmotic power.

Thermal Dependence of the Mesoscale Ionic Diode: Modeling and Experimental Verification.

Mesoscale ionic diodes, which can rectify ionic current at conditions at which their pore size is larger than 100 nm and thus over 100 times larger than the Debye length, have been recently discovered with potential applications in ionic circuits as well as osmotic power generation. Compared with the conventional nanoscale ionic diodes, the mesoscale ionic diodes can offer much higher conductance, ionic current resolution, and power generated. However, the thermal response, which has been proven playing a crucial role in nanofluidic devices, of the mesoscale ionic diode remains significantly unexplored. Here, we report the thermal dependence of the mesoscale ionic diode comprising a conical pore with a tip opening diameter of ∼400 nm. To capture its underlying physics more accurately, our model takes into account the practical equilibrium chemistry reaction of functional carboxyl groups on the pore surface. Modeling results predict that in the mesoscale ionic diode prepared currents increase but the performance decreases with the increase of temperature, which is consistent with our experimental data and indicates that the ion transport properties apparently depend on the presence of highly mobile hydroxide ions. The results gathered can provide important guidance for the design of new mesoscale ionic diodes, enriching their applications in thermoelectric power and thermoresponsive chemical sensors.

Unraveling the Anomalous Surface-Charge-Dependent Osmotic Power Using a Single Funnel-Shaped Nanochannel.

Nanofluidic osmotic power, which converts a difference in salinity between brine and fresh water into electricity with nanoscale channels, has received more and more attention in recent years. It is long believed that to gain high-performance osmotic power, highly charged channel materials should be exploited so as to enhance the ion selectivity. In this paper, we report counterintuitive surface-charge-density-dependent osmotic power in a single funnel-shaped nanochannel (FSN), violating the previous viewpoint. For the highly charged nanochannel, the performance of osmotic power decreases with a further increase in its surface charge density. With increasing pH (surface charge density), the FSN enables a local maximum power density as high as ∼3.5 kW/m2 in a 500 mM/1 mM KCl gradient. This observation is strongly supported by our rigorous model where the equilibrium chemical reaction between functional carboxylate ion groups on the channel wall and protons is taken into account. The modeling reveals that for a highly charged nanochannel, a significant increase in the surface charge density amplifies the ion concentration polarization effect, thus weakening the effective salinity ratio across the channel and undermining the osmotic power generated.