Nanofluidic Reverse Electrodialysis Research Articles

Advanced ion-selective wood membranes: Leveraging aligned cellulose nanofibers for enhanced osmotic energy conversion

Nanofluidic reverse electrodialysis (RED) is widely recognized as an exceptionally effective method for harvesting osmotic energy. Nevertheless, its progress has been impeded by the high costs and intricate fabrication processes associated with the required ion exchange membranes. The ion-selective wood membranes (ISWM) are derived directly from natural wood through a meticulously designed two-step chemical modification and densification process. The obtained ISWM with a highly charged surface effectively preserves the alignment of nanochannels from the cellulose fibers sourced in natural wood. Moreover, the laminated structure consisting of oriented nanofibers enhances ion conductivity by a factor of 4 compared to natural wood birch under low KCl concentrations. The charged and aligned nanochannels serve as nanofluidic conduits, facilitating selective ion transport. This, in turn, engenders efficient charge separation and the generation of an electrochemical potential difference. In energy harvesting systems such as ISWM-RED, the synergistic interplay between the electrochemical potential difference and ionic flux manifests in a remarkable output power density, reaching up to 658 mW m−2 to a salinity gradient of KCl at a magnitude of 50-fold. ISWM is an outstanding nanofluidic material that provides a cost-effective and easy-to-prepare solution for producing natural nanofluidic materials. Our investigation delineates a promising trajectory for developing high-performance nanofluidic RED devices tailored for efficient osmotic energy harvesting from renewable and abundant natural resources.

Efficient Solar-osmotic Power Generation from Bioinspired Anti-fouling 2D WS2 Composite Membranes.

Nanofluidic reverse electrodialysis provides an attractive way to harvest osmotic energy. However, most attention was paid to monotonous membrane structure optimization to promote selective ion transport, while the role of external fields and relevant mechanisms are rarely explored. Here, we demonstrate a Kevlar-toughened tungsten disulfide (WS2) composite membrane with bioinspired serosa-mimetic structures as an efficient osmotic energy generator coupling light. As a result, the output power could be up to 16.43 W m-2under irradiation, outperforming traditional two-dimensional (2D) membranes. Both the experiment and simulation uncover that the generated photothermal and photoelectronic effects could synergistically promote the confined ion transport process. In addition, this membrane also possesses great anti-fouling properties, endowing its practical application. This work paves new avenues for sustainable power generation by coupling solar energy.

Membranes for Osmotic Power Generation by Reverse Electrodialysis

In recent years, the utilization of the selective ion transport through porous membranes for osmotic power generation (blue energy) has received a lot of attention. The principal of power generation using the porous membranes is same as that of conventional reverse electrodialysis (RED), but nonporous ion exchange membranes are conventionally used for RED. The ion transport mechanisms through the porous and nonporous membranes are considerably different. Unlike the conventional nonporous membranes, the ion transport through the porous membranes is largely dictated by the principles of nanofluidics. This owes to the fact that the osmotic power generation via selective ion transport through porous membranes is often referred to as nanofluidic reverse electrodialysis (NRED) or nanopore-based power generation (NPG). While RED using nonporous membranes has already been implemented on a pilot-plant scale, the progress of NRED/NPG has so far been limited in the development of small-scale, novel, porous membrane materials. The aim of this review is to provide an overview of the membrane design concepts of nanofluidic porous membranes for NPG/NRED. A brief description of material design concepts of conventional nonporous membranes for RED is provided as well.

Synergy between ionic thermoelectric conversion and nanofluidic reverse electrodialysis for high power density generation

Nanofluidic reverse electrodialysis (NERD) is a promising method for the collections of salinity gradient energy. However, further improving the performance is necessary for the commercial applications, while only optimizing the nanopore structure and concentration ratio is hard to achieve the propose due to the tradeoff between high selectivity and low resistance in NERD systems. Based on ionic thermoelectric (i-TE) materials, which possessing huge Seebeck coefficient and natural ion channels, using the i-TE membrane and low-grade heat energy to introduce an additional driving force of temperature difference is proposed for the acceleration of ionic migrations. Results show that the effect of temperature difference is equivalent to overlaying an additional voltage difference, and then the synergy between i-TE conversion and NERD significantly enhances both the power density and efficiency. For the temperature differences of 10 K and Seebeck coefficient of 10 mV K−1, the power densities can be enhanced from 11.72 W/m2 to 23.4–93.8 W/m2, and the efficiencies can also be increased to nearly the upper limit of 0.5. Our study provides new roadmap for improving the NERD performance and the utilizing the low-grade heat energy.

Highly Efficient Osmotic Energy Harvesting in Charged Boron‐Nitride‐Nanopore Membranes

AbstractRecent studies of the high energy‐conversion efficiency of the nanofluidic platform have revealed the enormous potential for efficient exploitation of electrokinetic phenomena in nanoporous membranes for clean‐energy harvesting from salinity gradients. Here, nanofluidic reverse electrodialysis (NF‐RED) consisting of vertically aligned boron‐nitride‐nanopore (VA‐BNNP) membranes is presented, which can efficiently harness osmotic power. The power density of the VA‐BNNP reaches up to 105 W m−2, which is several orders of magnitude higher than in other nanopores with similar pore sizes, leading to 165 mW m−2 of net power density (i.e., power per membrane area). Low‐pressure chemical vapor deposition technology is employed to uniformly deposit a thin BN layer within 1D anodized alumina pores to prepare a macroscopic VA‐BNNP membrane with a high nanopore density, ≈108 pores cm−2. These membranes can resolve fundamental questions regarding the ion mobility, liquid transport, and power generation in highly charged nanopores. It is shown that the transference number in the VA‐BNNP is almost constant over the entire salt concentration range, which is different from other nanopore systems. Moreover, it is also demonstrated that the BN deposition on the nanopore channels can significantly enhance the diffusio‐osmosis velocity by two orders of magnitude at a high salinity gradient, resulting in a huge increase in power density.

Shape matters: Enhanced osmotic energy harvesting in bullet-shaped nanochannels

Nanofluidic reverse electrodialysis systems based on track-etched nanochannels are promising devices for new eco-friendly ways of sustainable energy generation. In recent years, several works have been focused on the influence of parameters such as pH, ionic strength, and chemical nature of the electrolyte on the device performance. However, despite the relevance of the geometry on the channel properties, the influence of the nanochannel shape on the performance of energy conversion remains almost unexplored. In this work, we present an experimental study – complemented with Poisson–Nernst–Planck simulations – that describes how the shape of the nanochannels strongly affects the energy conversion performance of single bullet-shaped nanochannels created on PET foils by the ion-track-etching method. To test optimal parameters for energy conversion and selectivity, the performance was investigated by varying the channel effective diameter as well as the pH and the electrolyte gradient. With a maximum output power of 80 pW, this system reveals the best value reported for a bare single track-etched nanochannel. Therefore, this work experimentally demonstrates that it is possible to obtain high power output by means of a careful choice of channel geometry and etching conditions, in addition to other experimental parameters such as pH and electrolyte gradient. We believe that these results offer a promising framework to explore new design concepts in nanofluidic osmotic power generators.

Hydrodynamic slip enhanced nanofluidic reverse electrodialysis for salinity gradient energy harvesting

Nanofluidic reverse electrodialysis offers an alternative way to harvest the widely-existing salinity gradient energy. In this study, we investigate the impacts of surface hydrodynamic slip modification on the ionic current rectification and salinity gradient energy conversion via a conical nanopore by thermodynamic analysis and numerical simulation. Results reveal that in the configuration where hydrodynamic slip modification is employed on the surface near the tip side, a small modification fraction contributes to the ionic current rectification due to significantly enhanced ion enrichment, while a larger hydrodynamic slip modification fraction goes against the ionic current rectification for deteriorated ion enhancement and induced counter-electric field concentration gradient near the base side. For energy conversion, at low concentration ratios, a large modification fraction brings an obvious augment on the electric power. However, it decreases energy conversion efficiency. At a concentration ratio of 100-fold, the electric power is increased by 60.7%, when half of the nanopore wall is modified into hydrodynamic slip. And the energy conversion efficiency is decreased by 6.41%. These findings shed light on the role of hydrodynamic slip modification on the ion transportation and salinity gradient energy conversion, and help developing high performance nanofluidic systems via hydrodynamic slip modifications.

Temperature regulated reverse electrodialysis in charged nanopores

Nanofluidic reverse electrodialysis (RED) is a promising way to utilize the vastly existed salinity gradient energy. In this paper, impacts of temperature gradient across the nanopore on the ion transportation and power generation performance are systematically investigated, and a theoretical description has been derived to illustrate the energy conversion efficiency under asymmetric temperatures. Results reveal that under isothermal reservoirs, the maximum power increases with increasing temperatures, while the corresponding efficiency presents no obvious difference due to synchronous enhancement of the cation and anion diffusive coefficients. For salt solutions under asymmetric temperatures, at small concentration ratios, the larger average temperature, the larger maximum power output due to augmented enhanced ion transportation. A negative temperature gradient contributes to the maximum power efficiency while the positive one decreases the maximum power efficiency. At large concentration ratios, the nanofluidic RED system exhibits different behaviours. A negative temperature gradient contributes to the maximum power and the corresponding efficiency while the positive one decreases the maximum power and the corresponding efficiency. The results in this paper may offer desirable guidance for improving nanofluidic RED performance.

Reverse electrodialysis in bilayer nanochannels: salinity gradient-driven power generation.

To evaluate the possibility of nano-fluidic reverse electrodialysis (RED) for salinity gradient energy harvesting, we consider the behavior of ion transportation in a bilayer cylindrical nanochannel consisting of different sized nanopores connecting two large reservoirs at different NaCl concentrations. Numerical simulations to illustrate the electrokinetic behavior at asymmetric sub-pore length and surface charge density are conducted, the impacts of which on transference number, osmotic current, diffusive voltage, maximum power and maximum power efficiency are systematically investigated. The results reveal that the transference number in Config. I (where high NaCl concentration is applied at the larger nanopore) is always larger than that in the opposite configuration (Config. II). At low concentration ratios, the osmotic current and maximum power have maximum values, while the maximum power efficiency decreases consistently. For Config. II, the ion transportation is impacted by the surface charge density at both sub-nanopores, while for Config. I, it is determined by the surface charge density at the downstream small nanopore. When large surface charge density is applied at the downstream small nanopore in contact with a very low concentration reservoir, there exists an interesting phenomenon: the larger surface charge density at the large nanopore induces a slight performance drop due to the impact of upstream EDL overlap.

Osmotic Power Generation with Positively and Negatively Charged 2D Nanofluidic Membrane Pairs

In nature, hierarchically assembled nanoscale ionic conductors, such as ion channels and ion pumps, become the structural and functional basis of bioelectric phenomena. Recently, ion‐channel‐mimetic nanofluidic systems have been built into reconstructed 2D nanomaterials for energy conversion and storage as effective as the electrogenic cells. Here, a 2D‐material‐based nanofluidic reverse electrodialysis system, containing cascading lamellar nanochannels in oppositely charged graphene oxide membrane (GOM) pairs, is reported for efficient osmotic energy conversion. Through preassembly modification, the surface charge polarity of the 2D nanochannels can be efficiently tuned from negative (−123 mC m−2) to positive (+147 mC m−2), yielding strongly cation‐ or anion‐selective GOMs. The complementary two‐way ion diffusion leads to an efficient charge separation process, creating superposed electrochemical potential difference and ionic flux. An output power density of 0.77 W m−2 is achieved by controlled mixing concentrated (0.5 m) and diluted ionic solutions (0.01 m), which is about 54% higher than using commercial ion exchange membranes. Tandem alternating GOM pairs produce high voltage up to 2.7 V to power electronic devices. Besides simple salt solutions, various complex electrolyte solutions can be used as energy sources. These findings provide insights to construct cascading nanofluidic circuits for energy, environmental, and healthcare applications.

Salinity gradient power: influences of temperature and nanopore size

Salinity gradient power is a promising, challenging, and readily available renewable energy. Among various methods for harvesting this clean energy, nanofluidic reverse electrodialysis (NRED) is of great potential. Since ionic transport depends highly on the temperature, so is the efficiency of the associated power generated. Here, we conduct a theoretical analysis on the influences of temperature and nanopore size on NRED, focusing on the temperature and nanopore size. The results gathered reveal that the maximum power increases with increasing temperature, but the conversion efficiency depends weakly on temperature. In general, the smaller the nanopore radius or the longer the nanopore, the better the ion selectivity. These results provide desirable and necessary information for improving the performance of NRED as well as designing relevant units in renewable energy plants.

Nanofluidic crystal: a facile, high-efficiency and high-power-density scaling up scheme for energy harvesting based on nanofluidic reverse electrodialysis

The great advances in nanotechnology call for advances in miniaturized power sources for micro/nano-scale systems. Nanofluidic channels have received great attention as promising high-power-density substitutes for ion exchange membranes for use in energy harvesting from ambient ionic concentration gradient, namely reverse electrodialysis. This paper proposes the nanofluidic crystal (NFC), of packed nanoparticles in micro-meter-sized confined space, as a facile, high-efficiency and high-power-density scaling-up scheme for energy harvesting by nanofluidic reverse electrodialysis (NRED). Obtained from the self-assembly of nanoparticles in a micropore, the NFC forms an ion-selective network with enormous nanochannels due to electrical double-layer overlap in the nanoparticle interstices. As a proof-of-concept demonstration, a maximum efficiency of 42.3 ± 1.84%, a maximum power density of 2.82 ± 0.22 W m−2, and a maximum output power of 1.17 ± 0.09 nW/unit (nearly three orders of magnitude of amplification compared to other NREDs) were achieved in our prototype cell, which was prepared within 30 min. The current NFC-based prototype cell can be parallelized and cascaded to achieve the desired output power and open circuit voltage. This NFC-based scaling-up scheme for energy harvesting based on NRED is promising for the building of self-powered micro/nano-scale systems.

Asymmetric Ion Transport through Ion-Channel-Mimetic Solid-State Nanopores

Both scientists and engineers are interested in the design and fabrication of synthetic nanofluidic architectures that mimic the gating functions of biological ion channels. The effort to build such structures requires interdisciplinary efforts at the intersection of chemistry, materials science, and nanotechnology. Biological ion channels and synthetic nanofluidic devices have some structural and chemical similarities, and therefore, they share some common features in regulating the traverse ionic flow. In the past decade, researchers have identified two asymmetric ion transport phenomena in synthetic nanofluidic structures, the rectified ionic current and the net diffusion current. The rectified ionic current is a diode-like current-voltage response that occurs when switching the voltage bias. This phenomenon indicates a preferential direction of transport in the nanofluidic system. The net diffusion current occurs as a direct product of charge selectivity and is generated from the asymmetric diffusion through charged nanofluidic channels. These new ion transport phenomena and the elaborate structures that occur in biology have inspired us to build functional nanofluidic devices for both fundamental research and practical applications. In this Account, we review our recent progress in the design and fabrication of biomimetic solid-state nanofluidic devices with asymmetric ion transport behavior. We demonstrate the origin of the rectified ionic current and the net diffusion current. We also identify several influential factors and discuss how to build these asymmetric features into nanofluidic systems by controlling (1) nanopore geometry, (2) surface charge distribution, (3) chemical composition, (4) channel wall wettability, (5) environmental pH, (6) electrolyte concentration gradient, and (7) ion mobility. In the case of the first four features, we build these asymmetric features directly into the nanofluidic structures. With the final three, we construct different environmental conditions in the electrolyte solutions on either side of the nanochannel. The novel and well-controlled nanofluidic phenomena have become the foundation for many promising applications, and we have highlighted several representative examples. Inspired by the electrogenic cell of the electric eel, we have demonstrated a proof-of-concept nanofluidic reverse electrodialysis system (NREDS) that converts salinity gradient energy into electricity by means of net diffusion current. We have also constructed chirality analysis systems into nanofluidic architectures and monitored these sensing events as the change in the degree of ionic current rectification. Moreover, we have developed a biohybrid nanosystem, in which we reconstituted the F0F1-ATPase on a liposome-coated, solid-state nanoporous membrane. By applying a transmembrane proton concentration gradient, the biohybrid nanodevice can synthesize ATP in vitro. These findings have improved our understanding of the asymmetric ion transport phenomena in synthetic nanofluidic systems and offer innovative insights into the design of functional nanofluidic devices.

Energy harvesting with bio-inspired synthetic nanochannels

With more than four billion years evolution and selection, natural creatures inherit almost perfect functional structures to harvesting clean energy from their living environments. Particularly, biological ion channels and pumps on cell membrane play a crucial role in many bioelectrogenesis processes. Learning from Nature, such as the electric eels, the synthesis of ATP molecules, the Bacteriorhodopsin on retina, etc, provides new approaches for the construction of novel energy conversion systems. In this review article, we briefly summarize the three most intensively studied topics on the clean energy conversion system with bio-inspired nanochannels and nanopores, which are the nanofluidic electrokinetic conversion systems, the nanofluidic reverse electrodialysis systems, and these newly arisen advanced energy conversion system with smart synthetic ion channels. In a predictable future, the performance of these bio-inspired energy conversion system will surly exceed the present achievements of the conventional man-made systems. The bio-mimetic and bio-inspired strategies provide new insights into future energy conversion techniques.

Towards understanding the nanofluidic reverse electrodialysis system: well matched charge selectivity and ionic composition

The widespread use of tiny electrical devices, from microelectromechanical systems (MEMS) to portable personal electronics, provides a new challenge in the miniaturization and integration of power supply systems. Towards this goal, we have recently demonstrated a bio-inspired nanofluidic energy harvesting system that converts salinity gradient energy from the ambient environment into sustainable electricity with single ion-selective nanopores (Adv. Funct. Mater. 2010, 20, 1339). The nanofluidic reverse electrodialysis system (NREDS) significantly improves the performance of conventional membrane-based reverse electrodialysis systems due to a higher ionic flux and a lower fluidic resistance. However, the fundamental working mechanism of the NREDS has been largely unexplored in the literature. In this work we have systematically investigated the performance of the NREDS in relation to the electrolyte type and the charge selectivity of the nanofluidic channel using both experimental and theoretical approaches. Experimental results show that the short-circuit current, the open-circuit voltage, and the resulting electric power of the NREDS are very sensitive to the ionic composition of the electrolyte solution. Through an in-depth theoretical analysis, two dominant factors that govern the charge separation and ion selectivity of the nanochannels were identified. The results prove that, with well-matched electrolyte types and nanopore charge selectivity, the harvested electric power and energy conversion efficiency can be improved by nearly two orders of magnitude.