Dual-Functional Super-Assembled Mesoporous Carbon-Titania/AAO Hetero-Channels for Bidirectionally Photo-Regulated Ion Transport

Photo-regulated nanofluidic devices have attracted great attention in recent years due to their adjustable ion transport in real time. However, most of the photo-responsive nanofluidic devices can only adjust the ionic current unidirectionally, and cannot simultaneously increase or decrease the current signal intelligently by one device. Herein, a mesoporous carbon-titania/ anodized aluminum hetero-channels (MCT/AAO) is constructed by super-assembly strategy, which exhibits dual-function of cation selectivity and photo response. The polymer and TiO₂ nanocrystals jointly build the MCT framework. Polymer framework with abundant negatively charged sites endows MCT/AAO with excellent cation selectivity, and TiO₂ nanocrystals are responsible for the photo-regulated ion transport. High photo current densities of 1.8 mA m⁻² (increase) and 1.2 mA m⁻² (decrease) are realized by MCT/AAO benefiting from the ordered hetero-channels. Significantly, MCT/AAO can also achieve the bidirectionally adjustable osmotic energy by alternating the configurations of concentration gradient. Theoretical and experimental results reveal that the superior photo-generated potential is responsible for the bidirectionally adjustable ion transport. Consequently, MCT/AAO performs the function of harvesting ionic energy from the equilibrium electrolyte solution, which greatly expands its practical application field. This work provides a new strategy in constructing dual-functional hetero-channels toward bidirectionally photo-regulated ionic transport and energy harvesting.     

Freestanding Lamellar Porous Carbon Stacks for Low‐Temperature‐Foldable Supercapacitors

High‐performance supercapacitors (SCs) are important energy storage components for emerging wearable electronics. Rendering low‐temperature foldability to SCs is critically important when wearable devices are used in a cold environment. However, currently reported foldable SCs do not have a stable electrochemical performance at subzero temperatures, while those that are performing are not foldable. Herein, a freestanding pure‐carbon‐based porous electrode, namely, lamellar porous carbon stack (LPCS), is reported, which enables stable low‐temperature‐foldable SCs. The LPCS, which is fabricated with a simple vacuum filtration of a mixture of carbon fibers (CFs), holey reduced graphene oxides (HRGOs), and carbon nanotubes (CNTs), possesses a lamellar stacking of porous carbon thin sheets, in which the CFs act as the skeleton and the HRGOs and CNTs act as binders. The unique structure leads to excellent compression resilience, high foldability, and high electronic and ionic conductivity. SCs made with the LPCS electrodes and ionic liquid electrolyte show a high energy density (2.1 mWh cm^?2 at 2 mA cm^?2), low‐temperature long lifetime (95% capacity after 10 000 cycles at ?30 °C), and excellent low‐temperature foldability (86% capacity after 1000 folding cycles at ?30 °C).     

Designing Nanofluidic Diode from a Hybrid-Bilayer Covalent Organic Framework: Molecular Simulation Investigation

Nanofluidic diodes are potentially useful in many important applications such as sensing, electronics, and energy conversion. However, the manufacturing of controllable nanopores for nanofluidic diodes is technically challenging. Herein, a nanofluidic diode is designed from a highly programmatic covalent organic framework (COF). Through molecular simulation, remarkable diode behavior is observed in a hybrid-bilayer COF but not in its constituent single-layer COFs. The rectification effect of ion current in the hybrid-bilayer COF is attributed to an asymmetric electrostatic potential across the COF nanopore. Furthermore, a synergistic effect of counterion is unraveled in the hybrid-bilayer COF, and the presence of counterion is found to reduce the entry barrier and facilitate ion transport. The performance of the hybrid-bilayer COF as a nanofluidic diode is comprehensively investigated by varying salt concentration, layer number, interlayer spacing, and slipping. This proof-of-concept simulation study demonstrates the feasibility of the hybrid-bilayer COF as a nanofluidic diode and the finding may stimulate the development of new nanofluidic platforms.     

Light‐Powered Directional Nanofluidic Ion Transport in Kirigami‐Made Asymmetric Photonic‐Ionic Devices

Nacre‐mimetic 2D nanofluidic materials with densely packed sub‐nanometer‐height lamellar channels find widespread applications in water‐, energy‐, and environment‐related aspects by virtue of their scalable fabrication methods and exceptional transport properties. Recently, light‐powered nanofluidic ion transport in synthetic materials gained considerable attention for its remote, noninvasive, and active control of the membrane transport property using the energy of light. Toward practical application, a critical challenge is to overcome the dependence on inhomogeneous or site‐specific light illumination. Here, asymmetric photonic‐ionic devices based on kirigami‐tailored graphene oxide paper are fabricated, and directional nanofluidic ion transport properties therein powered by full‐area light illumination are demonstrated. The in‐plane asymmetry of the graphene oxide paper is essential to the generation of photoelectric driving force under homogeneous illumination. This light‐powered ion transport phenomenon is explained based on a modified carrier diffusion model. In asymmetric nanofluidic structures, enhanced recombination of photoexcited charge carriers at the membrane boundary breaks the electric potential balance in the horizontal direction, and thus drives the ion transport in that direction under symmetric illumination. The kirigami‐based strategy provides a facile and scalable way to fabricate paper‐like photonic‐ionic devices with arbitrary shapes, working as fundamental elements for large‐scale light‐harvesting nanofluidic circuits.     

Anchoring Pt Particles onto Mesoporousized ZnO Holey Cubes for Triethylamine Detection with Multifaceted Superiorities

Designing sensing materials with integrating unique spatial structures, functional units, and surface activity is vital to achieve high-performance gas sensor toward triethylamine (TEA) detection. Herein, a simple spontaneous dissolution is used with subsequent thermal decomposition strategy to fabricate mesoporousized ZnO holey cubes. The squaric acid is crucial to coordinate Zn²⁺ to form a cubic shape (ZnO-0) and then tailor the inner part to open a holey cube with simultaneously mesoporousizing the left cubic body (ZnO-72). To enhance the sensing performance, the mesoporous ZnO holey cubes have been functionalized with catalytic Pt nanoparticles, which deliver superior performances including high response, low detection limit, and fast response and recovery time. Notably, the response of Pt/ZnO-72 towards 200 ppm TEA is up to 535, which is much higher than those of 43 and 224 for pristine ZnO-0 and ZnO-72. A synergistic mechanism combining the intrinsic merits of ZnO, its unique mesoporous holey cubic structure, the oxygen vacancies, and the catalytic sensitization effect of Pt has been proposed for the significant enhancement in TEA sensing. Our work provides an effective facile approach to fabricate an advanced micro-nano architecture with manipulating its spatial structure, functional units, and active mesoporous surface for promising TEA gas sensors.     

Electrokinetic Energy Conversion in Self‐Assembled 2D Nanofluidic Channels with Janus Nanobuilding Blocks

Inspired by the microstructure of nacre, material design, and large‐scale integration of artificial nanofluidic devices step into a completely new stage, termed 2D nanofluidics, in which mass and charge transportation are confined in the interstitial space between reconstructed 2D nanomaterials. However, all the existing 2D nanofluidic systems are reconstituted from homogeneous nanobuilding blocks. Herein, this paper reports the bottom‐up construction of 2D nanofluidic materials with kaolinite‐based Janus nanobuilding blocks, and demonstrates two types of electrokinetic energy conversion through the network of 2D nanochannels. Being different from previous 2D nanofluidic systems, two distinct types of sub‐nanometer‐ and nanometer‐wide fluidic channels of about 6.8 and 13.8 Å are identified in the reconstructed kaolinite membranes (RKM), showing prominent surface‐governed ion transport behaviors and nearly perfect cation‐selectivity. The RKMs exhibit superior capability in osmotic and hydraulic energy conversion, compared to graphene‐based membranes. The mineral‐based 2D nanofluidic system opens up a new avenue to self‐assemble asymmetric 2D nanomaterials for energy, environmental, and healthcare applications.     

DNA translocation in inorganic nanotubes

Inorganic nanotubes were successfully integrated with microfluidic systems to create nanofluidic devices for single DNA molecule sensing. Inorganic nanotubes are unique in their high aspect ratio and exhibit translocation characteristics in which the DNA is fully stretched. Transient changes of ionic current indicate DNA translocation events. A transition from current decrease to current enhancement during translocation was observed on changing the buffer concentration, suggesting interplay between electrostatic charge and geometric blockage effects. These inorganic nanotube nanofluidic devices represent a new platform for the study of single biomolecule translocation with the potential for integration into nanofluidic circuits.     

Highly Efficient Ionic Photocurrent Generation through WS2‐Based 2D Nanofluidic Channels

The unique feature of nacre‐like 2D layered materials provides a facile, yet highly efficient way to modulate the transmembrane ion transport from two orthogonal transport directions, either vertical or horizontal. Recently, light‐driven active transport of ionic species in synthetic nanofluidic systems attracts broad research interest. Herein, taking advantage of the photoelectric semiconducting properties of 2D transition metal dichalcogenides, the generation of a directional and greatly enhanced cationic flow through WS₂‐based 2D nanofluidic membranes upon asymmetric visible light illumination is reported. Compared with graphene‐based materials, the magnitude of the ionic photocurrent can be enhanced by tens of times, and its photo‐responsiveness can be 2–3.5 times faster. This enhancement is explained by the coexistence of semiconducting and metallic WS₂ nanosheets in the hybrid membrane that facilitates the asymmetric diffusion of photoexcited charge carriers on the channel wall, and the high ionic conductance due to the neat membrane structure. To further demonstrate its application, photonic ion switches, photonic ion diodes, and photonic ion transistors as the fundamental elements for light‐controlled nanofluidic circuits are further developed. Exploring new possibilities in the family of liquid processable colloidal 2D materials provides a way toward high‐performance light‐harvesting nanofluidic systems for artificial photosynthesis and sunlight‐driven desalination.     

Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors

In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film is prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance with maximum specific capacitance of 670 F cm^?3 (134 mF cm^?2), due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as‐prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder‐free electrode effectively reduce electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provide a high specific surface area to improve electron transport, enhancing rapid ion transport, and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/microsize electronic devices.     

“Salting out” in Hofmeister Effect Enhancing Mechanical and Electrochemical Performance of Amide-based Hydrogel Electrolytes for Flexible Zinc-Ion Battery

With the development of flexible and wearable electronic devices, it is a new challenge for polymer hydrogel electrolytes to combine high mechanical flexibility and electrochemical performance into one membrane. In general, the high content of water in hydrogel electrolyte membranes always leads to poor mechanical strength, and limits their applications in flexible energy storage devices. In this work, based on the “salting out” phenomenon in Hofmeister effect, a kind of gelatin-based hydrogel electrolyte membrane is fabricated with high mechanical strength and ionic conductivity by soaking pre-gelated gelatin hydrogel in 2 m ZnSO₄ aqueous. Among various gelatin-based electrolyte membranes, the gelatin-ZnSO₄ electrolyte membrane delivers the “salting out” property of Hofmeister effect, which improves both the mechanical strength and electrochemical performance of gelatin-based electrolyte membranes. The breaking strength reaches 1.5 MPa. When applied to supercapacitors and zinc-ion batteries, it can sustain over 7500 and 9300 cycles for repeated charging and discharging processes. This study provides a very simple and universal method to prepare polymer hydrogel electrolytes with high strength, toughness, and stability, and its applications in flexible energy storage devices provide a new idea for the construction of secure and stable flexible and wearable electronic devices.     

High Ion Conductive and Selective Membrane Achieved through Dual Ion Conducting Mechanisms

Conventional ion-selective membranes, that is ion-exchange and porous membranes, are unable to perform high conductivity and selectivity simultaneously due to the contradictions between their ion selecting and conducting mechanisms. In this work, a bifunctional ion-selective layer is developed via the combination of nanoporous boron nitride (PBN) and ion exchange groups from Nafion to achieve high ion conductivity through dual ion conducting mechanisms as well as high ion selectivity. A template-free method is adopted to synthesize flake-like PBN, which is further enmeshed with Nafion resin to form the bifunctional layer coated onto a porous polyetherimide membrane. The double-layer membrane exhibits excellent ion selectivity (1.49 × 10⁸ mS cm⁻³ min), which is 22 times greater than that of the pristine porous polyetherimide membrane, with outstanding ion conductivity (64 mS cm⁻¹). In a vanadium flow battery, the double-layer membrane achieves a high Coulombic efficiency of 97% and outstanding energy efficiency of 91% at 40 mA cm⁻² with a stable cycling performance for over 700 cycles at 100 mA cm⁻². PBN with ion exchange groups may therefore offer a potential solution to the limitation between ion selectivity and conductivity in ion-selective membranes.     

Rectified ion transport through concentration gradient in homogeneous silica nanochannels

We investigate the ionic rectifying effect through 4 and 20 nm thick silica nanochannels placed between two ionic solutions of different concentrations. The effect was observed when only a single side of the channel has electric double-layer overlap. The calculation based on Poisson-Nernst-Planck (PNP) theory and a simplified model suggests that the phenomenon result from the accumulation and depletion of both cations and anions in the nanochannels responding to different bias polarities. The model also elucidates that the basis of the rectifying effects in the nanofluidic devices reported to date is due to the asymmetric cation/anion ratios or equivalently built-in potentials on the two sides of the nanochannels. The study benefits the design of nanofluidic devices for attoliter-scale chemical delivery.     

Bioderived Ionic Liquids with Alkaline Metal Ions for Transient Ionics

Choline lactate, an ionic liquid composed of bioderived materials, offers an opportunity to develop biodegradable electrochemical devices. Although ionic liquids possess large potential windows, high conductivity, and are nonvolatile, they do not exhibit electrochemical characteristics such as intercalation pseudocapacitance, redox pseudocapacitance, and electrochromism. Herein, bioderived ionic liquids are developed, including metal ions, Li, Na, and Ca, to yield ionic liquid with electrochemical behavior. Differential scanning calorimetry results reveal that the ionic liquids remained in liquid state from 230.42 to 373.15 K. The conductivities of the ionic liquids with metal are lower than those of the pristine ionic liquid, whereas the capacitance change negligibly. A protocol of the Organization for Economic Co-operation and Development 301C modified MITI test (I) confirms that the pristine ionic liquid and ionic liquids with metal are readily biodegradable. Additionally, an ionic gel comprising the ionic liquid and poly(vinyl alcohol) is biodegradable. An electrochromic device is developed using an ionic liquid containing Li ions. The device successfully changes color at −2.5 V, demonstrating the intercalation of Li ions into the WO₃ crystal. The results suggest that the electrochemically active ionic liquids have potential for the development of environmentally benign devices, sustainable electronics, and bioresorbable/implantable devices.     

Enhancing the anti-cracking performance of perfluorosulfonic acid membranes for implantable biosensors through supercritical CO<Subscript>2</Subscript> treatment

Due to the outstanding stability, biocompatibility, and permeability, perfluorosulfonic acid (PFSA) membranes can be used to protect biosensors in biological environment. However, mineralization induced cracking hinders their in vivo applications for long duration. Various methods including anneal, preincubation in FeCl₃ solution, and layer-by-layer self assembly were attempted to improve their anti-cracking performance, but only met with limited success. In this study, a new method, namely supercritical carbon dioxide (Sc-CO₂) treatment was developed to enhance the anti-cracking performance of PFSA membranes. After being incubated in cell culture medium for 12 weeks, while the pristine membranes undergone intense cracking, their Sc-CO₂ treated counterparts kept almost intact. Small-angle X-ray scattering and wide-angle X-ray diffraction results revealed the more perfect structure in the treated membranes. Meanwhile, the crystalline structure of pristine membranes was obviously destroyed after cultivation, whereas the treated membranes exhibited little change. The increased crystallinity and reduced ionic clusters size of the Sc-CO₂ treated membranes are responsible to the greatly enhanced anti-cracking performance. In addition, such improvement paves the way for the applications of PFSA membranes in implantable biosensors.     

Free‐Standing Holey Ni(OH)2 Nanosheets with Enhanced Activity for Water Oxidation

Electrochemical water oxidation is the key technology in water‐splitting reactions and rechargeable metal–air batteries, which is very attractive for renewable energy conversion and storage. Replacement of precious catalysts with cost‐effective and highly active alternatives is still a great challenge. Herein, based on theoretical predictions, holey structures are designed and fabricated on the free‐standing conventional 2D OER catalyst. By well‐controlled defects engineering, uniform tiny holes are created on the free‐standing Ni(OH)₂ nanosheets via a sol–gel method, with the embedded Zn components as the template for holes production. The whole preparation process is feasible and effective to make full use of the basal plane of 2D nanomaterials, which can provide higher surface area, richer defects, more grain boundaries, and edge sites, as well as greater distorted surfaces. Meanwhile, these holes developed inside the sheet structure can supply tremendous permeable channels for ions adsorption and transportation, enable a fast interfacial charge transfer and accelerate the reaction process. The as‐prepared 2D holey Ni(OH)₂ nanostructures exhibit excellent catalytic performance toward electrochemical water oxidation, with lower onset overpotentials and higher current densities compared with the pristine Ni(OH)₂ catalyst, suggesting the holey defects engineering is a promising strategy for efficient water‐splitting devices and rechargeable metal–air batteries.     

Charged Layered Boron Nitride‐Nanoflake Membranes for Efficient Ion Separation and Water Purification

2D layered nanomaterials have attracted considerable attention for their potential for highly efficient separations, among other applications. Here, a 2D lamellar membrane synthesized using hexagonal boron nitride nanoflakes (h‐BNF) for highly efficient ion separation is reported. The ion‐rejection performance and the water permeance of the membrane as a function of the ionic radius, ion valance, and solution pH are investigated. The nonfunctionalized h‐BNF membranes show excellent ion rejection for small sized salt ions as well as for anionic dyes (>97%) while maintaining a high water permeability, ≈1.0 × 10^?3 L m m^?2 h^?1 bar^?1). Experiments show that the ion‐rejection performance of the membrane can be tuned by changing the solution pH. The results also suggest that the rejection is influenced by the ionic size and the electrostatic repulsion between fixed negative charges on the BN surface and the mobile ions, and is consistent with the Donnan equilibrium model. These simple‐to‐fabricate h‐BNF membranes show a unique combination of excellent ion selectivity and high permeability compared to other 2D membranes.     

Extrusion‐Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL^?1) can be readily achieved. The shear‐thinning behavior of the aqueous hGO ink enables extrusion‐based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4–25 nm through‐holes on hGO sheets), microscale (tens of micrometer‐sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high‐performance energy storage devices that rely on interfacial reactions to promote full active‐site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive‐free architectures are demonstrated as the first 3D printed lithium–oxygen (Li–O₂) cathodes and characterized alongside 3D printed GO‐based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high‐energy‐density battery systems.     

Light‐Driven Active Proton Transport through Photoacid‐ and Photobase‐Doped Janus Graphene Oxide Membranes

Biological electrogenic systems use protein‐based ionic pumps to move salt ions uphill across a cell membrane to accumulate an ion concentration gradient from the equilibrium physiological environment. Toward high‐performance and robust artificial electric organs, attaining an antigradient ion transport mode by fully abiotic materials remains a great challenge. Herein, a light‐driven proton pump transport phenomenon through a Janus graphene oxide membrane (JGOM) is reported. The JGOM is fabricated by sequential deposition of graphene oxide (GO) nanosheets modified with photobase (BOH) and photoacid (HA) molecules. Upon ultraviolet light illumination, the generation of a net protonic photocurrent through the JGOM, from the HA‐GO to the BOH‐GO side, is observed. The directional proton flow can thus establish a transmembrane proton concentration gradient of up to 0.8 pH units mm^?2 membrane area at a proton transport rate of 3.0 mol h^?1 m^?2. Against a concentration gradient, antigradient proton transport can be achieved. The working principle is explained in terms of asymmetric surface charge polarization on HA‐GO and BOH‐GO multilayers triggered by photoisomerization reactions, and the consequent intramembrane proton concentration gradient. The implementation of membrane‐scale light‐harvesting 2D nanofluidic system that mimics the charge process of the bioelectric organs makes a straightforward step toward artificial electrogenic and photosynthetic applications.     

Scalable Fabrication of MXene-PVDF Nanocomposite Triboelectric Fibers via Thermal Drawing

In the data-driven world, textile is a valuable resource for improving the quality of life through continuous monitoring of daily activities and physiological signals of humans. Triboelectric nanogenerators (TENG) are an attractive option for self-powered sensor development by coupling energy harvesting and sensing ability. In this study, to the best of the knowledge, scalable fabrication of Ti₃C₂T_x MXene-embedded polyvinylidene fluoride (PVDF) nanocomposite fiber using a thermal drawing process is presented for the first time. The output open circuit voltage and short circuit current show 53% and 58% improvement, respectively, compared to pristine PVDF fiber. The synergistic interaction between the surface termination groups of MXene and polar PVDF polymer enhances the performance of the fiber. The flexibility of the fiber enables the weaving of fabric TENG devices for large-area applications. The fabric TENG (3 × 2 cm²) demonstrates a power density of 40.8 mW m⁻² at the matching load of 8 MΩ by maintaining a stable performance over 12 000 cycles. Moreover, the fabric TENG has shown the capability of energy harvesting by operating a digital clock and a calculator. A distributed self-powered sensor for human activities and walking pattern monitoring are demonstrated with the fabric.