Enhanced nanofluidic transport in activated carbon nanoconduits.

Carbon has emerged as a unique material in nanofluidics, with reports of fast water transport, molecular ion separation and efficient osmotic energy conversion. Many of these phenomena still await proper rationalization due to the lack of fundamental understanding of nanoscale ionic transport, which can only be achieved in controlled environments. Here we develop the fabrication of 'activated' two-dimensional carbon nanochannels. Compared with nanoconduits with 'pristine' graphite walls, this enables the investigation of nanoscale ionic transport in great detail. We show that activated carbon nanochannels outperform pristine channels by orders of magnitude in terms of surface electrification, ionic conductance, streaming current and (epi-)osmotic currents. A detailed theoretical framework enables us to attribute the enhanced ionic transport across activated carbon nanochannels to an optimal combination of high surface charge and low friction. Furthermore, this demonstrates the unique potential of activated carbon for energy harvesting from salinity gradients with single-pore power density across activated carbon nanochannels, reaching hundreds of kilowatts per square metre, surpassing alternative nanomaterials.

Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF3), which has a nonlayered, rhombohedral structure and therefore cannot  possibly be obtained by exfoliation. The conversion of InSe into InF3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

Tunable sieving of ions using graphene oxide membranes.

Graphene oxide membranes show exceptional molecular permeation properties, with promise for many applications. However, their use in ion sieving and desalination technologies is limited by a permeation cutoff of ∼9 Š(ref. 4), which is larger than the diameters of hydrated ions of common salts. The cutoff is determined by the interlayer spacing (d) of ∼13.5 Å, typical for graphene oxide laminates that swell in water. Achieving smaller d for the laminates immersed in water has proved to be a challenge. Here, we describe how to control d by physical confinement and achieve accurate and tunable ion sieving. Membranes with d from ∼9.8 Što 6.4 Šare demonstrated, providing a sieve size smaller than the diameters of hydrated ions. In this regime, ion permeation is found to be thermally activated with energy barriers of ∼10-100 kJ mol-1 depending on d. Importantly, permeation rates decrease exponentially with decreasing sieve size but water transport is weakly affected (by a factor of <2). The latter is attributed to a low barrier for the entry of water molecules and large slip lengths inside graphene capillaries. Building on these findings, we demonstrate a simple scalable method to obtain graphene-based membranes with limited swelling, which exhibit 97% rejection for NaCl.