Interfacial Super-Assembly of Vacancy Engineered Ultrathin-Nanosheets Toward Nanochannels for Smart Ion Transport and Salinity Gradient Power Conversion.

Ion-selective nanochannel membranes assembled from two-dimensional (2D) nanosheets hold immense promise for power conversion using salinity gradient. However, they face challenges stemming from insufficient surface charge density, which impairs both permselectivity and durability. Herein, we present a novel vacancy-engineered, oxygen-deficient NiCo layered double hydroxide (NiCoLDH)/cellulose nanofibers-wrapped carbon nanotubes (VOLDH/CNF-CNT) composite membrane. This membrane, featuring abundant angstrom-scale, cation-selective nanochannels, is designed and fabricated through a synergistic combination of vacancy engineering and interfacial super-assembly. The composite membrane shows interlayer free-spacing of ~3.62 Å, which validates the membrane size exclusion selectivity. This strategy, validated by DFT calculations and experimental data, improves hydrophilicity and surface charge density, leading to the strong interaction with K+ ions to benefit the low ion transport resistance and exceptional charge selectivity. When employed in an artificial river water|seawater salinity gradient power generator, it delivers a high-power density of 5.35 W/m2 with long-term durability (20,000s), which is almost 400 % higher than that of the pristine NiCoLDH membrane. Furthermore, it displays both pH- and temperature-sensitive ion transport behavior, offering additional opportunities for optimization. This work establishes a basis for high-performance salinity gradient power conversion and underscores the potential of vacancy engineering and super-assembly in customizing 2D nanomaterials for diverse advanced nanofluidic energy devices.

Interfacial Super-Assembly of Intertwined Nanofibers toward Hybrid Nanochannels for Synergistic Salinity Gradient Power Conversion.

Capturing the abundant salinity gradient power into electric power by nanofluidic systems has attracted increasing attention and has shown huge potential to alleviate the energy crisis and environmental pollution problems. However, not only the imbalance between permeability and selectivity but also the poor stability and high cost of traditional membranes limit their scale-up realistic applications. Here, intertwined "soft-hard" nanofibers/tubes are densely super-assembled on the surface of anodic aluminum oxide (AAO) to construct a heterogeneous nanochannel membrane, which exhibits smart ion transport and improved salinity gradient power conversion. In this process, one-dimensional (1D) "soft" TEMPO-oxidized cellulose nanofibers (CNFs) are wrapped around "hard" carbon nanotubes (CNTs) to form three-dimensional (3D) dense nanochannel networks, subsequently forming a CNF-CNT/AAO hybrid membrane. The 3D nanochannel networks constructed by this intertwined "soft-hard" nanofiber/tube method can significantly enhance the membrane stability while maintaining the ion selectivity and permeability. Furthermore, benefiting from the asymmetric structure and charge polarity, the hybrid nanofluidic membrane displays a low membrane inner resistance, directional ionic rectification characteristics, outstanding cation selectivity, and excellent salinity gradient power conversion performance with an output power density of 3.3 W/m2. Besides, a pH sensitive property of the hybrid membrane is exhibited, and a higher power density of 4.2 W/m2 can be achieved at a pH of 11, which is approximately 2 times more compared to that of pure 1D nanomaterial based homogeneous membranes. These results indicate that this interfacial super-assembly strategy can provide a way for large-scale production of nanofluidic devices for various fields including salinity gradient energy harvesting.