Responsive Protection of Magnesium Alloys From Multicorrosive Media by Constructing Nanofluidic Channels in Self-Repairing Coatings.

Low-density magnesium (Mg) alloys are excellent engineering materials, and can significantly reduce energy consumption by replacing existing steel and aluminum materials. However, Mg species are susceptible to corrosion, especially in harsh environments (high-temperature or acidic), severely limiting the range of practical applications. Here, 2D covalent organic framework (COF) is synthesized with pore diameters ranging from 1.5 to 2.9 nm to obtain ultrafast nanofluidic channels. Loaded with silver (Ag+) ions, 2-mercaptobenzimidazole (2-MB) inhibitors are immobilized in the COF channels through the silver bridges. Based on the strong metal-complexing capability, Ag+ ions precipitated with various corrosive media (Cl-, Br-, I-, SO3 2-, S2-, S2O3 2- SO4 2-, CO3 2-, PO4 3-); meanwhile, the 2-MB inhibitors are rapidly released through the nanofluidic channels, forming a passivation film as a corrosion barrier to protect the Mg substrate. After integration with commercial polyethersulfone (PES), the COF-based coating exhibits high repairing capability achieving 100% damage restoration within 7 h, outperforming all existing coatings of Mg alloys. Notably, the coating shows almost complete protection of Mg alloys after being treated in respective 473 K, acidic (pH ≈4.0), and alkaline (pH ≈10.0) environments.

Designing Nanofluidic Channels of Boron Nitride Nanosheets/Aramid Nanofibers/Covalent Organic Frameworks Nanofiltration Membrane for Ultrafast Mass Transport.

2D lamellar nanofiltration membrane is considered to be a promising approach for desalinating seawater/brackish water and recycling sewage. However, its practical feasibility is severely constrained by the lack of durability and stability. Herein, a ternary nanofiltration membrane via a mixed-dimensional assembly of 2D boron nitride nanosheets (BNNS) is fabricated, 1D aramid nanofibers (ANF), and 2D covalent organic frameworks (COF). The abundant 2D and 1D nanofluid channels endow the BNNS/ANF/COF membrane with a high flux of 194 L·m‒2·h‒1. By the synergies of the size sieving and Donnan effect, the BNNS/ANF/COF membrane demonstrates high rejection (among 98%) for those dyes whose size exceeds 1.0 nm. Moreover, the BNNS/ANF/COF membrane also exhibits remarkable durability and mechanical stability, which are attributed to the strong adhesion and interactions between BNNS, ANF, and COF, as well as the superior mechanical robustness of ANF. This work provides a novel strategy to develop robust and durable 2D lamellar nanofiltration membranes with high permeance and selectivity simultaneously.

From Sheep Track to Motorway: Supramolecular-Mediated 2D Nanofluidic Channels for Ultrafast Water Transport.

Atomic thick 2D materials hold great potential as building blocks to construct highly permeable membranes, yet the permeability of laminar 2D material membranes is still limited by their irregularity sheep track-like interlayer channels. Herein, a supramolecular-mediated strategy to induce the regular assembly of high-throughput 2D nanofluidic channels based on host-guest interactions is proposed. Inspired by the characteristics of motorways, supramolecular-mediated ultrathin 2D membranes with broad and continuous regular water transport channels are successfully constructed using graphene oxide (GO) as an example. The prepared membrane achieves an ultrahigh water permeability (369.94 LMH bar-1) more than six times higher than that of the original membranes while maintaining dye rejection above 98.5%, which outperforms the reported 2D membranes. Characterization and simulation results show that the introduction of hyaluronate-grafted ß-cyclodextrin not only expands the interlayer channels of GO membranes but also enables the membranes to operate stably under harsh conditions with the help of host-guest interactions. This universal supramolecular assembly strategy provides new opportunities for the preparation of 2D membranes with high separation performance and reliable and stable nanofluidic channels.

High Strength MXene/PBONF Heterogeneous Membrane with Excellent Ion Selectivity for Efficient Osmotic Energy Conversion.

Layered MXene nanofluidic membranes still face the problems of low mechanical property, poor ion selectivity, and low output power density. In this work, we successfully constructed heterostructured membranes with the combination of the layered channels of the MXene layer on the top and the nanoscale poly(p-phenylene-benzodioxazole) nanofiber (PBONF) layer on the bottom through a stepwise filtration method. The as-prepared MXene/PBONF-50 heterogeneous membrane exhibits high mechanical properties (strength of 221.6 MPa, strain of 3.2%), high ion selectivity of 0.87, and an excellent output power density of 15.7 W/m2 at 50-fold concentration gradient. Excitingly, the heterogeneous membrane presents a high power density of 6.8 W/m2 at a larger testing area of 0.79 mm2 and long-term stability. This heterogeneous membrane construction provides a viable strategy for the enhancement of mechanical properties and osmotic energy conversion of 2D materials.

Flexible Glass-Based Hybrid Nanofluidic Device to Enable the Active Regulation of Single-Molecule Flows.

Single-molecule studies offer deep insights into the essence of chemistry, biology, and materials science. Despite significant advances in single-molecule experiments, the precise regulation of the flow of single small molecules remains a formidable challenge. Herein, we present a flexible glass-based hybrid nanofluidic device that can precisely block, open, and direct the flow of single small molecules in nanochannels. Additionally, this approach allows for real-time tracking of regulated single small molecules in nanofluidic conditions. Therefore, the dynamic behaviors of single small molecules confined in different nanofluidic conditions with varied spatial restrictions are clarified. Our device and approach provide a nanofluidic platform and mechanism that enable single-molecule studies and applications in actively regulated fluidic conditions, thus opening avenues for understanding the original behavior of individual molecules in their natural forms and the development of single-molecule regulated chemical and biological processes in the future.

Surfactant-Assisted Sulfonated Covalent Organic Nanosheets: Extrinsic Charge for Improved Ion Transport and Salinity-Gradient Energy Harvesting.

Charge-governed ion transport is the vital property of nanofluidic channels for salinity-gradient energy harvesting and other electrochemical energy conversion technologies. 2D nanofluidic channels constructed by nanosheets exhibit great superiority in ion selectivity, but a high ion transport rate remains challenging due to the insufficiency of intrinsic surface charge density in nanoconfinement. Herein, extrinsic surface charge into nanofluidic channels composed of surfactant-assisted sulfonated covalent organic nanosheets (SCONs), which enable tunable ion transport behaviors, is demonstrated. The polar moiety of surfactant is embedded in SCONs to adjust in-plane surface charges, and the aggregation of nonpolar moiety results in the sol-to-gel transformation of SCON solution for membrane fabrication. The combination endows SCON/surfactant membranes with considerable water-resistance, and the designable extrinsic charges promise fast ion transport and high ion selectivity. Additionally, the SCON/surfactant membrane, serving as a power generator, exhibits huge potential in harvesting salinity-gradient energy where corresponding output power density can reach up to 9.08 W m-2 under a 50-fold salinity gradient (0.5 m NaCl|0.01 m NaCl). The approach to extrinsic surface charge provides new and promising insight into regulating ion transport behaviors.

Precise Cation Recognition in Two-Dimensional Nanofluidic Channels of Clay Membranes Imparted from Intrinsic Selectivity of Clays.

Various kinds of clays occur naturally and are accompanied by particular cations in their interlayer domains. Here we report the reassembled membranes with nanofluidic channel arrays by using the natural clays montmorillonite, mica, and vermiculite, which were imparted with the natural selectivity for realizing precise recognition and directional regulation of the naturally occurring interlayer cations. A typical surface-governed ionic transport behavior was observed in the clay nanofluidic channels. Through asymmetric structural modification, cationic current rectification was realized in montmorillonite channels that performed as a nanofluidic diode. Interestingly, in the mica nanofluidic channel, the K+ that was naturally occurring in the interlayer domain of mica showed a reciprocating motion and resulted in a periodically fluctuating current. Electrodialysis demonstrated that such a fluctuating current reflects a directional selectivity for K+, achieving at least a 6000 times permeation rate difference with Li+ ions. The specific selectivity for Li+/Mg2+ on vermiculite reached up to 856 times with similar cations by the current technique. As-obtained clay membranes possess application prospects in energy conversion, brine resource development, etc. Such a strategy can achieve the designed selectivity through systematic screening of the building blocks, thus imparting them with the inherent characteristics of natural clays, which provides an alternative solution to the present manufacture of selective membranes.

Anion-Selective Layered Double Hydroxide Composites-Based Osmotic Energy Conversion for Real-Time Nutrient Solution Detection.

Nanofluidic channels based on 2D nanomaterials are promising to harvest osmotic energy for their high ion selectivity and osmotic conductivity. However, anion-selective nanofluidic channels are rare and chemical modification is necessary through fabrication. Here, a naturally anion-selective composite membrane is reported, that is, NiAl-Layered double hydroxide (LDH) coated anodic aluminum oxide (LDH@AAO), using a simple precipitant-free in situ growth technique. Positively charged LDH plates growing in channels of AAO function as screening layers for anions. Both experiments and theoretical simulations are enforced to certify the vital role of LDH growth in ion distribution and salinity gradient energy conversion. The composite membrane achieves high output performance and long-term stability. Furthermore, novel applications of nanofluidic channels are explored in hydroponic production and design a real-time detecting system based on LDH@AAO composite membranes for nutrient solution. This work provides insights into naturally anion-selective nanofluidic channels for osmotic energy harvesting and broadens the application in agricultural information sensing.

Development of a Mechanically Flexible 2D-MXene Membrane Cathode for Selective Electrochemical Reduction of Nitrate to N2: Mechanisms and Implications.

The contamination of water resources by nitrate is a major problem. Herein, we report a mechanically flexible 2D-MXene (Ti3C2Tx) membrane with multilayered nanofluidic channels for a selective electrochemical reduction of nitrate to nitrogen gas (N2). At a low applied potential of -0.8 V (vs Ag/AgCl), the MXene electrochemical membrane was found to exhibit high selectivity for NO3- reduction to N2 (82.8%) due to a relatively low desorption energy barrier for the release of adsorbed N2 (*N2) compared to that for the adsorbed NH3 (*NH3) based on density functional theory (DFT) calculations. Long-term use of the MXene membrane for treating 10 mg-NO3-N L-1 in water was found to have a high faradic efficiency of 72.6% for NO3- reduction to N2 at a very low electrical cost of 0.28 kWh m-3. Results of theoretical calculations and experimental results showed that defects on the MXene nanosheet surfaces played an important role in achieving high activity, primarily at the low-coordinated Ti sites. Water flowing through the MXene nanosheets facilitated the mass transfer of nitrate onto the low-coordinated Ti sites with this enhancement of particular importance under cathodic polarization of the MXene membrane. This study provides insight into the tailoring of nanoengineered materials for practical application in water treatment and environmental remediation.

Engineering 2D Nanofluidic Li-Ion Transport Channels for Superior Electrochemical Energy Storage.

Rational surface engineering of 2D nanoarchitectures-based electrode materials is crucial as it may enable fast ion transport, abundant-surface-controlled energy storage, long-term structural integrity, and high-rate cycling performance. Here we developed the stacked ultrathin Co3 O4 nanosheets with surface functionalization (SUCNs-SF) converted from layered hydroxides with inheritance of included anion groups (OH- , NO3- , CO32- ). Such stacked structure establishes 2D nanofluidic channels offering extra lithium storage sites, accelerated Li-ion transport, and sufficient buffering space for volume change during electrochemical processes. Tested as an anode material, this unique nanoarchitecture delivers high specific capacity (1230 and 1011 mAh g-1 at 0.2 and 1 A g-1 , respectively), excellent rate performance, and long cycle capability (1500 cycles at 5 A g-1 ). The demonstrated advantageous features by constructing 2D nanochannels in nonlayered materials may open up possibilities for designing high-power lithium ion batteries.

Biomimetic multifunctional nanochannels based on the asymmetric wettability of heterogeneous nanowire membranes.

A charged heterogeneous nanowire membrane with asymmetric wettability serves as a biomimetic passive channel when the bilayer is hydrophilic; It also functions as pH valve based on the hydrophobic CaWO4 layer (contact angle of 145.3˚±0.3˚) and hydrophilic MnO2 layer. Moreover, a reversible ionic rectification is realized in the above-mentioned semi-hydrophobic and hydrophilic state with strong acid environment or in the complete hydrophobic stage with a moderate discrepancy (CA of CaWO4 and MnO2 layer are 141.3˚±0.3˚ and 157.6˚±2.0˚, respectively) in near neuter condition.