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

Recent 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.     

In Situ Growth of Imine-Bridged Anion-Selective COF/AAO Membrane for Ion Current Rectification and Nanofluidic Osmotic Energy Conversion

Facing the energy crisis, using the salinity gradient between seawater and freshwater for osmotic energy conversion is a direct way to obtain energy. So far, most nanofluidic membranes utilized for osmotic energy generation are cation-selective. Given that both anion- and cation-selective membranes have the identical importance for energy conversion devices, it is of great significance to develop anion-selective membranes. Herein, an anion-selective membrane is synthesized by in situ growth of imine-bridged covalent organic framework (COF) on ordered anodic aluminum oxide (AAO) at room temperature. The imine groups and residual amino groups of COF can combine with protons in neutral solution, enabling the COF positively charged and efficiently transport of anions. Particularly, due to the asymmetry in the charge and structure of COF/AAO, the as-prepared membrane exhibits excellent ionic current rectification property, which can inhibit ion concentration polarization effectively and possess high ion selectivity and permeability. Using the present COF/AAO membrane, salinity gradient energy can be successfully harvested from solutions with high salt content, and the output power density reached 17.95W m⁻² under a 500-fold salinity gradient. The study provides a new avenue for construction and application of anion-selective membranes in the smart ion transport and efficient energy conversion.     

Anomalous Channel‐Length Dependence in Nanofluidic Osmotic Energy Conversion

Recent advances in materials science and nanotechnology have lead to considerable interest in constructing ion‐channel‐mimetic nanofluidic systems for energy conversion and storage. The conventional viewpoint suggests that to gain high electrical energy, the longitudinal dimension of the nanochannels (L) should be reduced so as to bring down the resistance for ion transport and provide high ionic flux. Here, counterintuitive channel‐length dependence is described in nanofluidic osmotic power generation. For short nanochannels (with length L < 400 nm), the converted electric power persistently decreases with the decreasing channel length, showing an anomalous, non‐Ohmic response. The combined thermodynamic analysis and numerical simulation prove that the excessively short channel length impairs the charge selectivity of the nanofluidic channels and induces strong ion concentration polarization. These two factors eventually undermine the osmotic power generation and its energy conversion efficiency. Therefore, the optimal channel length should be between 400 and 1000 nm in order to maximize the electric power, while balancing the efficiency. These findings reveal the importance of a long‐overlooked element, the channel length, in nanofluidic energy conversion and provide guidance to the design of high‐performance nanofluidic energy devices.     

Integrating Ionic Gate and Rectifier Within One Solid‐State Nanopore via Modification with Dual‐Responsive Copolymer Brushes

A dual‐functional nanofluidic device is demonstrated that integrates the ionic gate and the ionic rectifier within one solid‐state nanopore. The functionalities are realized by fabricating temperature‐ and pH‐responsive poly(N‐isopropyl acrylamide‐co‐acrylic acid) brushes onto the wall of a cone‐shaped nanopore. At ca. 25 °C, the nanopore works on a low ion conducting state. When the temperature is raised to ca. 40 °C, the nanopore switches to a high ion conducting state. The closing/opening of the nanopore results from the temperature‐triggered conformational transition of the attached copolymer brushes. Independently, in neutral and basic solutions, the conical nanopore rectifies the ionic current. While in acid solutions, no ion rectifying properties can be found. The charge properties of the copolymer brushes, combined with the asymmetrical pore geometry, render the nanopore a pH‐tunable ionic rectifier. The chemical modification strategy could be applied to incorporate other stimuli‐responsive materials for designing smart multi‐functional nanofluidic systems resembling the “live” creatures in nature.     

Paper-Mill Waste Reinforced Nanofluidic Membrane as High-Performance Osmotic Energy Generators

Nanofluidic membranes consisting of 2D materials and polymers are considered promising candidates for harvesting osmotic energy from river estuaries owing to their unique ion channels. However, micron-scale polymer chains agglomerate in the nanochannels, resulting in steric hindrance and affection ion transport. Herein, a nanofluidic membrane is designed from MXene and xylan nanoparticles that are derived from paper-mill waste. The demonstrated membrane reinforced by paper-mill waste has the characteristics of green, low-cost, and outstanding performance in mechanical properties and surface-charge-governed ionic transport. The MXene/carboxmethyl xylan (CMX) membrane demonstrates a high surface charge (ζ-potential of −44.3 mV) and 12 times higher strength (284.96 MPa) than the pristine MXene membrane. The resulting membrane shows intriguing features of high surface charge, high ion selectivity, and reduced steric hindrance, enabling it high osmotic energy generation performance. A potential of the nanofluidic membrane is ≈109 mV, the corresponding current of up to 2.73 µA, and the output power density of 14.52 mW m⁻² are obtained under a 1000-fold salt concentration gradient. As the electrolyte pH increases, the power density reaches 56.54 mW m⁻². This works demonstrate that CMX nanoparticles can effectively enhance the properties of the nanofluidic membrane and provide a promising strategy to design high-performance nanofluidic devices.     

Zwitterionic Gradient Double-Network Hydrogel Membranes with Superior Biofouling Resistance for Sustainable Osmotic Energy Harvesting

Developing ion-selective membranes with anti-biofouling property and biocompatibility is highly crucial in harvesting osmotic energy in natural environments and for future biomimetic applications. However, the exploration of membranes with these properties in osmotic energy conversion remain largely unaddressed. Herein, a tough zwitterionic gradient double-network hydrogel membrane (ZGDHM) with excellent biofouling resistance and cytocompatibility for sustainable osmotic energy harvesting is demonstrated. The ZGDHM, composed of negatively charged 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as the first scaffold network and zwitterionic sulfobetaine acrylamide (SBAA) as the second network, is prepared by a two-step photopolymerization, thus creating continuous gradient double-network nanoarchitecture and then remarkably enhanced mechanical properties. As verified by the experiments and simulations, the gradient nanoarchitecture endows the hydrogel membrane with apparent ionic diode effect and space-charge-governed transport property, thus facilitating directional ion transport. Consequently, the ZGDHM can achieve a power density of 5.44 W m⁻² by mixing artificial seawater and river water, surpassing the commercial benchmark. Most importantly, the output power can be promoted to an unprecedented value of 49.6 W m⁻² at the mixing of salt-lake water and river water, nearly doubling up most of the existing nanofluidic membranes. This study paves a new avenue toward developing ultrahigh-performance osmotic energy harvesters for biomimetic applications.     

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.     

High-Strength,Thin PBO Nanofiber Membrane with Long-Term Stability for Osmotic Energy Conversion

Ion-selective membrane embedded in a reverse electrodialysis system can achieve the conversion of osmotic energy into electricity. However, the ingenious design and development of pure polymer membranes that simultaneously satisfy excellent mechanical strength, long-term stability, high power density, and increased testing area is a crucial challenge. Here, high-strength, thin PBO nanofiber membranes (PBONM) with 3D nanofluidic channels and a thickness of 0.81 µm are prepared via a simple vacuum-assisted filtration technology. The thin PBONM exhibits excellent mechanical properties: stress of 235.8 MPa and modulus of 16.96 GPa, outperforming the state-of-the-art nanofluidic membranes. The obtained PBONM reveals surface-charge-governed ion transport behavior and high ion selectivity of 0.88 at a 50-fold concentration gradient. The PBO membrane-based generator delivers a power density of 7.7 and 40.2 W m⁻² at 50-fold and 500-fold concentration gradient. Importantly, this PBONM presents excellent stability in response to different external environments including various saline solutions, pH, and temperature. In addition, the maximum power density of PBONM reaches up to 5.9 W m⁻² under an increased testing area of 0.79 mm², exceeding other membrane-based generators with comparable testing areas. This work paves the way for constructing high-strength fiber nanofluidic membranes for highly efficient osmotic energy conversion.     

Microwave Combustion for Rapidly Synthesizing Pore‐Size‐Controllable Porous Graphene

Porous graphene has been widely applied in energy storage, electrocatalysis, photoelectron devices, etc. However, the producing process for porous graphene usually needs long time and is a tedious step. In this work, porous graphene is prepared with controllable pore size by using active metal nanoparticles to catalytically oxidize carbon under microwave combustion process within tens of seconds. The ion exchange membrane based on porous graphene with ≈5 nm pore diameter exhibits a great performance for salinity gradient power generation application with a power density output of ≈1.15 W m^?2. This work highlights a new strategy for the design and synthesis of pore‐size‐controllable porous graphene and provides new opportunities for 2D porous nanomaterials.     

Heterogeneous MXene/PS-b-P2VP Nanofluidic Membranes with Controllable Ion Transport for Osmotic Energy Conversion

Membrane-based osmotic power harvesting is a strategy for sustainable power generation. 2D nanofluids with high ion conductivity and selectivity are emerging candidates for osmotic energy conversion. However, the ion diffusion under nanoconfinement is hindered by homogeneous 2D membranes with monotonic charge regulation and severe concentration polarization, which results in an undesirable power conversion performance. Here, an asymmetric nanochannel membrane with a two-layered structure is reported, in which the angstrom-scale channels of 2D transition metal carbides/nitrides (MXenes) act as a screening layer for controlling ion transport, and the nanoscale pores of the block copolymer (BCP) are the pH-responsive arrays with an ordered nanovoid structure. The heterogeneous nanofluidic device exhibits an asymmetric charge distribution and enlarged 1D BCP porosity under acidic and alkaline conditions, respectively; this improves the gradient-driven ion diffusion, allowing a high-performance osmotic energy conversion with a power density of up to 6.74 W m⁻² by mixing artificial river water and seawater. Experiments and theoretical simulations indicate that the tunable asymmetric heterostructure contributes to impairing the concentration polarization and enhancing the ion flux. This efficient osmotic energy generator can advance the fundamental understanding of the MXene-based heterogeneous nanofluidic devices as a paradigm for membrane-based energy conversion technologies.     

Laterally Heterogeneous 2D Layered Materials as an Artificial Light‐Harvesting Proton Pump

Heterogeneous structures in nacre‐mimetic 2D layered materials generate novel transport phenomena in angstrom range, and thus provide new possibilities for innovative applications for sustainable energy, a clean environment, and human healthcare. In the two orthogonal transport directions, either vertical or horizontal, heterostructures in horizontal direction have never been reported before. Here, a 2D‐material‐based laterally heterogeneous membrane is fabricated via an unconventional dual‐flow filtration method. Negatively and positively charged graphene oxide multilayers are laterally patterned and interconnected in a planar configuration. Upon visible light illumination on the bipolar nanofluidic heterojunction, protons are able to move uphill against their concentration gradient, functioning as a light‐harvesting proton pump. A maximum proton concentration gradient of about 5.4 pH units mm^?2 membrane area can be established at a transport rate up to 14.8 mol h^?1 m^?2. The transport mechanism can be understood as a light‐triggered asymmetric polarization in surface potential and the consequent change in proton capacity in separate parts. The implementation of photonic–ionic conversion with abiotic materials provides a full‐solid‐state solution for bionic vision and artificial photosynthesis. There is plenty of room to expect the laterally heterogeneous membranes for new functions and better performance in the abundant family of liquid processable colloidal 2D materials.     

Topologically Programmed Graphene Oxide Membranes with Bioinspired Superstructures toward Boosting Osmotic Energy Harvesting

The emergence of lamellar nanofluidic membranes offers feasible routes for developing highly efficient, mechanically robust, and large-scale devices for osmotic energy harvesting. However, inferior ion permeability associated with their relatively long channels limits ionic flux and restricts their output performance. Herein, a superstructured graphene oxide membrane is developed to allow programmable topological variation in local geometry and contain laminar spaces inside. Such deliberate design offers excess specific area as well as nanofluidic channels to modulate transmembrane ionic transportation while concomitantly retaining similar nanoconfined environment in contrast to planar ones, leading to considerable enhancement of ionic permeability without compromising selectivity. This can be highly favorable in terms of osmotic energy harvesting, where the superstructured membranes offer a power output much higher than those of conventional planar ones. Besides, the superstructure design also endows the resulting membranes with benign biofouling resistance, which can be crucial to their long-term usage in converting osmotic energy. This study highlights the importance of membrane topographies and presents a general design concept that could be extended to other nanoporous membranes to develop high-performance nanofluidic devices.     

On the Origin of Ion Selectivity in Ultrathin Nanopores: Insights for Membrane‐Scale Osmotic Energy Conversion

Nanopores in ultrathin or atomically thin membranes attract broad interest because the infinitesimal pore depth allows selective transport of ions and molecules with ultimate permeability. Toward large‐scale osmotic energy conversion, great challenges remain in extrapolating the promising single‐pore demonstration to really powerful macroscopic applications. Herein, the origin of the selective ion transport in ultrathin nanopores is systematically investigated. Based on a precise Poisson and Nernst–Planck model calculation, it is found that the generation of net diffusion current and membrane potential stems from the charge separation within the electric double layer on the outer membrane surface, rather than that on the inner pore wall. To keep the charge selectivity of the entire membrane, a critical surface charged area surrounding each pore orifice is therefore highly demanded. Otherwise, at high pore density, the membrane selectivity and the overall power density would fall down instead, which explains the giant gap between the actual experimental achievements and the single‐pore estimation. To maximize the power generation, smaller nanopores (pore diameter ≈1–2 nm) are appropriate for large‐scale osmotic energy conversion. With a porosity of ≈10%, the total power density approaches more than 200 W m^‐2, anticipating a substantial advance toward high‐performance large‐scale nanofluidic power sources.     

Atom‐Thick Membranes for Water Purification and Blue Energy Harvesting

Membrane‐based processes, namely, water purification and harvesting of osmotic power deriving from the difference in salinity between seawater and freshwater are two strategic research fields holding great promise for overcoming critical global issues such as the world growing energy demand, climate change, and access to clean water. Ultrathin membranes based on 2D materials (2DMs) are particularly suitable for highly selective separation of ions and effective generation of blue energy because of their unique physicochemical properties and novel transport mechanisms occurring at the nano‐ and sub‐nanometer length scale. However, due to the relatively high costs of fabrication compared to traditional porous membrane materials, their technological transfer toward large‐scale applications still remains a great challenge. Herein, the authors present an overview of the current state‐of‐the‐art in the development of ultrathin membranes based on 2DMs for osmotic power generation and water purification. The authors discuss several synthetic routes to produce atomically thin membranes with controlled porosity and describe in detail their performance, with a particular emphasis on pressure‐retarded osmosis and reversed electrodialysis methods. In the last section, an outlook and current limitations as well as viable future developments in the field of 2DM membranes are provided.     

Fingerprint‐Inspired Conducting Hierarchical Wrinkles for Energy‐Harvesting E‐Skin

In the field of bionics, sophisticated and multifunctional electronic skins with a mechanosensing function that are inspired by nature are developed. Here, an energy‐harvesting electronic skin (energy‐E‐skin), i.e., a pressure sensor with energy‐harvesting functions is demonstrated, based on fingerprint‐inspired conducting hierarchical wrinkles. The conducting hierarchical wrinkles, fabricated via 2D stretching and subsequent Ar plasma treatment, are composed of polydimethylsiloxane (PDMS) wrinkles as the primary microstructure and embedded Ag nanowires (AgNWs) as the secondary nanostructure. The structure and resistance of the conducting hierarchical wrinkles are deterministically controlled by varying the stretching direction, Ar plasma power, and treatment time. This hierarchical‐wrinkle‐based conductor successfully harvests mechanical energy via contact electrification and electrostatic induction and also realizes self‐powered pressure sensing. The energy‐E‐skin delivers an average output power of 3.5 mW with an open‐circuit voltage of 300 V and a short‐circuit current of 35 µA; this power is sufficient to drive commercial light‐emitting diodes and portable electronic devices. The hierarchical‐wrinkle‐based conductor is also utilized as a self‐powered tactile pressure sensor with a sensitivity of 1.187 mV Pa^‐1 in both contact‐separation mode and the single‐electrode mode. The proposed energy‐E‐skin has great potential for use as a next‐generation multifunctional artificial skin, self‐powered human–machine interface, wearable thin‐film power source, and so on.     

Fabrication of Bio‐Inspired 2D MOFs/PAA Hybrid Membrane for Asymmetric Ion Transport

Biological ion channels are known as membrane proteins which can turn on and off under environmental stimulus to regulate ion transport and energy conversion. Rapid progress made in biological ion channels provides inspiration for developing artificial nanochannels to mimic the structures and functions of ion transport systems and energy conversion in biological ion channels. Due to the advantages of abundant pore channels, metal–organic frameworks (MOFs) have become competitive materials to control the nanofluidic transport. Herein, a facile in situ synthesis method is developed to prepare hybrid nanochannels constructed by 2D MOFs and porous anodic aluminum (PAA). The introduction of asymmetries in the chemical composition and surface charge properties gives the hybrid outstanding ion current rectification properties and excellent ion selectivity. A power density of 1.6 W m^?2 is achieved by integrating it into a salinity‐gradient‐driven device. With advantages of facile fabrication method and high ion selectivity, the prepared 2D MOFs/PAA hybrid membrane offers a promising candidate for power conversion and water desalination.     

Photoinduced Directional Proton Transport through Printed Asymmetric Graphene Oxide Superstructures: A New Driving Mechanism under Full‐Area Light Illumination

2D‐material‐based membranes with densely packed sub‐nanometer‐height fluidic channels show exceptional transport properties, and have attracted broad research interest for energy‐, environment‐, and healthcare‐related applications. Recently, light‐controlled active transport of ionic species in abiotic materials have received renewed attention. However, its dependence on inhomogeneous or site‐specific illumination is a challenge for scalable application. Here, directional proton transport through printed asymmetric graphene oxide superstructures (GOSs) is demonstrated under full‐area illumination. The GOSs are composed of partially stacked graphene oxide multilayers formed by a two‐step direct ink writing process. The direction of the photoinduced proton current is determined by the position of top graphene oxide multilayers, which functions as a photogate to modulate the horizontal ion transport through the beneath lamellar nanochannels. This transport phenomenon unveils a new driving mechanism that, in asymmetric nanofluidic structures, the decay of local light intensity in depth direction breaks the balance of electric potential distribution in horizontal direction, and thus generates a photoelectric driving force for ion transport. Following this mechanism, the GOSs are developed into photonic ion transistors with three different gating modes. The asymmetrically printed photonic‐ionic devices provide fundamental elements for light‐harvesting nanofluidic circuits, and may find applications for artificial photosynthesis and artificial electric organs.     

High‐Performance Flexible Thermoelectric Devices Based on All‐Inorganic Hybrid Films for Harvesting Low‐Grade Heat

The fabrication of a flexible thermoelectric (TE) device that contains flexible, all‐inorganic hybrid thin films (p‐type single‐wall carbon nanotubes (SWCNTs)/Sb₂Te₃ and n‐type reduced graphene oxide (RGO)/Bi₂Te₃) is reported. The optimized power factors of the p‐type and n‐type hybrid thin films at ambient temperature are about 55 and 108 µW m^?1 K^?2, respectively. The high performance of these films that are fabricated through the combination of vacuum filtration and annealing can be attributed to their planar orientation and network structure. In addition, a TE device, with 10 couples of legs, shows an output power of 23.6 µW at a temperature gradient of 70 K. A prototype of an integrated photovoltaic‐TE (PV‐TE) device demonstrates the ability to harvest low‐grade “waste” thermal energy from the human body and solar irradiation. The flexible TE and PV‐TE device have great potential in wearable energy harvesting and management.     

Maximized Effective Energy Output of Contact‐Separation‐Triggered Triboelectric Nanogenerators as Limited by Air Breakdown

Recent progress in triboelectric nanogenerators (TENGs) has demonstrated their promising potential as a high‐efficiency mechanical energy harvesting technology, and plenty of effort has been devoted to improving the power output by maximizing the triboelectric surface charge density. However, due to high‐voltage air breakdown, most of the enhanced surface charge density brought by material/surface optimization or external ion injection is not retainable or usable for electricity generation during the operation of contact‐separation‐triggered TENGs. Here, the existence of the air breakdown effect in a contact‐separation mode TENG with a low threshold surface charge density of ≈40–50 µC m^?2 is first validated under the high impedance external load, and then followed by the theoretical study of the maximized effective energy output as limited by air breakdown for contact‐separation‐triggered TENGs. The effects of air pressure and gas composition are also studied and propose promising solutions for reducing the air breakdown effect. This research provides a crucial fundamental study for TENG technology and its further development and applications.     

Single‐Thread‐Based Wearable and Highly Stretchable Triboelectric Nanogenerators and Their Applications in Cloth‐Based Self‐Powered Human‐Interactive and Biomedical Sensing

The development of wearable and large‐area fabric energy harvester and sensor has received great attention due to their promising applications in next‐generation autonomous and wearable healthcare technologies. Here, a new type of “single” thread‐based triboelectric nanogenerator (TENG) and its uses in elastically textile‐based energy harvesting and sensing have been demonstrated. The energy‐harvesting thread composed by one silicone‐rubber‐coated stainless‐steel thread can extract energy during contact with skin. With sewing the energy‐harvesting thread into a serpentine shape on an elastic textile, a highly stretchable and scalable TENG textile is realized to scavenge various kinds of human‐motion energy. The collected energy is capable to sustainably power a commercial smart watch. Moreover, the simplified single triboelectric thread can be applied in a wide range of thread‐based self‐powered and active sensing uses, including gesture sensing, human‐interactive interfaces, and human physiological signal monitoring. After integration with microcontrollers, more complicated systems, such as wireless wearable keyboards and smart beds, are demonstrated. These results show that the newly designed single‐thread‐based TENG, with the advantage of interactive, responsive, sewable, and conformal features, can meet application needs of a vast variety of fields, ranging from wearable and stretchable energy harvesters to smart cloth‐based articles.