Layer-by-layer Assembly of Nanosheets with Matching Size and Shape for More Stable Membrane Structure than Nanosheet-Polymer Assembly.

Layer-by-layer (LbL) assembly of oppositely charged materials has been widely used as an approach to make two-dimensional (2D) nanosheet-based membranes, which often involves 2D nanosheets being alternately deposited with polymer-based polyelectrolytes to obtain an electrostabilized nanosheet-polymer structure. In this study, we hypothesized that using 2D nanosheets with matching physical properties as both polyanions and polycations may result in a more ordered nanostructure with better stability than a nanosheet-polymer structure. To compare the differences between nanosheet-nanosheet vs nanosheet-polymer structures, we assembled negatively charged molybdenum disulfide nanosheets (MoS2) with either positively charged graphene oxide (PrGO) nanosheets or positively charged polymer (PDDA). Using combined measurements by ellipsometer and quartz crystal microbalance with dissipation, we discovered that the swelling of MoS2-PrGO in ionic solutions was 60% lower than that of MoS2-PDDA membranes. Meanwhile, the MoS2-PrGO membrane retained its permeability upon drying, whereas the permeability of MoS2-PDDA decreased by 40% due to the restacking of MoS2. Overall, the MoS2-PrGO membrane demonstrated a better filtration performance. Additionally, our X-ray photoelectron spectroscopy results and analysis on layer density revealed a clearer transition in material composition during the LbL synthesis of MoS2-PrGO membranes, and the X-ray diffraction pattern suggested its resemblance to an ordered, layer-stacked structure. In conclusion, the MoS2-PrGO membrane made with nanosheets with matching size, shape, and charge density exhibited a much more aligned stacking structure, resulting in reduced membrane swelling under high salinity solutions, controlled restacking, and improved separation performance.

Interplay of the forces governing steroid hormone micropollutant adsorption in vertically-aligned carbon nanotube membrane nanopores.

Vertically-aligned carbon nanotube (VaCNT) membranes allow water to conduct rapidly at low pressures and open up the possibility for water purification and desalination, although the ultralow viscous stress in hydrophobic and low-tortuosity nanopores prevents surface interactions with contaminants. In this experimental investigation, steroid hormone micropollutant adsorption by VaCNT membranes is quantified and explained via the interplay of the hydrodynamic drag and friction forces acting on the hormone, and the adhesive and repulsive forces between the hormone and the inner carbon nanotube wall. It is concluded that a drag force above 2.2 × 10-3 pN overcomes the friction force resulting in insignificant adsorption, whereas lowering the drag force from 2.2 × 10-3 to 4.3 × 10-4 pN increases the adsorbed mass of hormones from zero to 0.4 ng cm-2. At a low drag force of 1.6 × 10-3 pN, the adsorbed mass of four hormones is correlated with the hormone-wall adhesive (van der Waals) force. These findings explain micropollutant adsorption in nanopores via the forces acting on the micropollutant along and perpendicular to the flow, which can be exploited for selectivity.

Ion and Hydrodynamic Translucency in 1D van der Waals Heterostructured Boron-Nitride Single-Walled Carbon Nanotubes.

An unresolved challenge in nanofluidics is tuning ion selectivity and hydrodynamic transport in pores, particularly for those with diameters larger than a nanometer. In contrast to conventional strategies that focus on changing surface functionalization or confinement degree by varying the radial dimension of the pores, we explore a unique approach for manipulating ion selectivity and hydrodynamic flow enhancement by externally coating single-walled carbon nanotubes (SWCNTs) with a few layers of hexagonal boron nitride (h-BN). For van der Waals heterostructured BN-SWCNTs, we observed a 9-fold increase in cation selectivity for K+ versus Cl- compared to pristine SWCNTs of the same 2.2 nm diameter, while hydrodynamic slip lengths decreased by more than an order of magnitude. These results suggest that the single-layer graphene inner surface may be translucent to charge-regulation and hydrodynamic-slip effects arising from h-BN on the outside of the SWCNT. Such 1D heterostructures could serve as synthetic platforms with tunable properties for exploring distinct nanofluidic phenomena and their potential applications.

Fast Water Transport through Subnanometer Diameter Vertically Aligned Carbon Nanotube Membranes.

Small-diameter carbon nanotubes (CNTs) have outstanding mass-transport properties, especially enhanced water flow. Here, we report on water transport through the first macroscopic membranes with vertically oriented, subnanometer (0.8 nm) CNT pores, made by a scalable, solution-based method with electric-field alignment of bulk-grown single-wall CNTs (SWCNTs). After plasma etching to open pores, vertically aligned CNTs served as the primary pathway for liquid-water transport. The CNT membranes showed fast pressure-driven water transport, with up to 105-fold enhancement compared to no-slip Hagen-Poiseuille flow. Comparing 0.8 and 3 nm CNTs, we found that the hydrodynamic slip lengths increased with decreasing nanotube diameter, reaching 8.5 µm for the smaller-diameter CNTs. The results suggest that pressure-driven water transport in small-diameter CNTs is increasingly dominated by entrance resistance, thus becoming independent of nanotube length. Scalably fabricated membranes incorporating vertically aligned subnanometer CNT pores could have applications in water filtration, desalination, and energy harvesting.

Modifying the Molecular Structure of Carbon Nanotubes through Gas-Phase Reactants.

Current approaches to carbon nanotube (CNT) synthesis are limited in their ability to control the placement of atoms on the surface of nanotubes. Some of this limitation stems from a lack of understanding of the chemical bond-building mechanisms at play in CNT growth. Here, we provide experimental evidence that supports an alkyne polymerization pathway in which short-chained alkynes directly incorporate into the CNT lattice during growth, partially retaining their side groups and influencing CNT morphology. Using acetylene, methyl acetylene, and vinyl acetylene as feedstock gases, unique morphological differences were observed. Interwall spacing, a highly conserved value in natural graphitic materials, varied to accommodate side groups, increasing systematically from acetylene to methyl acetylene to vinyl acetylene. Furthermore, attenuated total reflectance Fourier-transfer infrared spectroscopy (ATR-FTIR) illustrated the existence of intact methyl groups in the multiwalled CNTs derived from methyl acetylene. Finally, the nanoscale alignment of the CNTs grown in vertically aligned forests differed systematically. Methyl acetylene induced the most tortuous growth while CNTs from acetylene and vinyl-acetylene were more aligned, presumably due to the presence of polymerizable unsaturated bonds in the structure. These results demonstrate that feedstock hydrocarbons can alter the atomic-scale structure of CNTs, which in turn can affect properties on larger scales. This information could be leveraged to create more chemically and structurally complex CNT structures, enable more sustainable chemical pathways by avoiding the need for solvents and postreaction modifications, and potentially unlock experimental routes to a host of higher-order carbonaceous nanomaterials.

Differences in water and vapor transport through angstrom-scale pores in atomically thin membranes.

The transport of water through nanoscale capillaries/pores plays a prominent role in biology, ionic/molecular separations, water treatment and protective applications. However, the mechanisms of water and vapor transport through nanoscale confinements remain to be fully understood. Angstrom-scale pores (~2.8-6.6 Å) introduced into the atomically thin graphene lattice represent ideal model systems to probe water transport at the molecular-length scale with short pores (aspect ratio ~1-1.9) i.e., pore diameters approach the pore length (~3.4 Å) at the theoretical limit of material thickness. Here, we report on orders of magnitude differences (~80×) between transport of water vapor (~44.2-52.4 g m-2 day-1 Pa-1) and liquid water (0.6-2 g m-2 day-1 Pa-1) through nanopores (~2.8-6.6 Å in diameter) in monolayer graphene and rationalize this difference via a flow resistance model in which liquid water permeation occurs near the continuum regime whereas water vapor transport occurs in the free molecular flow regime. We demonstrate centimeter-scale atomically thin graphene membranes with up to an order of magnitude higher water vapor transport rate (~5.4-6.1 × 104 g m-2 day-1) than most commercially available ultra-breathable protective materials while effectively blocking even sub-nanometer (>0.66 nm) model ions/molecules.

Growth and Performance of High-Quality SWCNT Forests on Inconel Foils as Lithium-Ion Battery Anodes.

Large-scale production of vertically aligned single-walled carbon nanotubes (VA-SWCNTs) on metal foils promises to enable technological advancements in many fields, from functional composites to energy storage to thermal interfaces. In this work, we demonstrate growth of high-quality (G/D > 6, average diameters ∼ 2-3 nm, densities > 1012 cm-2) VA-SWCNTs on Inconel metal for use as a lithium-ion battery (LIB) anode. Scale-up of SWCNT growth on Inconel 625 to 100 cm2 exhibits nearly invariant CNT structural properties, even when synthesis is performed near atmospheric pressure, and this robustness is attributed to a growth kinetic regime dominated by the carbon precursor diffusion in the bulk gas mixture. SWCNT forests produced on large-area metal substrates at close to atmospheric pressure possess a combination of structural features that are among the best demonstrated so far in the literature for growth on metal foils. Leveraging these achievements for energy applications, we demonstrate a VA-SWCNT LIB anode with capacity >1200 mAh/g at 1.0C and stable cycling beyond 300 cycles. This robust synthesis of high-quality VA-SWCNTs on metal foils presents a promising route toward mass production of high-performance CNT devices for a broad range of applications.

Fast Permeation of Small Ions in Carbon Nanotubes.

Simulations and experiments have revealed enormous transport rates through carbon nanotube (CNT) channels when a pressure gradient drives fluid flow, but comparatively little attention has been given to concentration-driven transport despite its importance in many fields. Here, membranes are fabricated with a known number of single-walled CNTs as fluid transport pathways to precisely quantify the diffusive flow through CNTs. Contrary to early experimental studies that assumed bulk or hindered diffusion, measurements in this work indicate that the permeability of small ions through single-walled CNT channels is more than an order of magnitude higher than through the bulk. This flow enhancement scales with the ion free energy of transfer from bulk solutions to a nanoconfined, lower-dielectric environment. Reported results suggest that CNT membranes can unlock dialysis processes with unprecedented efficiency.

Ultra-Permeable Single-Walled Carbon Nanotube Membranes with Exceptional Performance at Scale.

Enhanced fluid transport in single-walled carbon nanotubes (SWCNTs) promises to enable major advancements in many membrane applications, from efficient water purification to next-generation protective garments. Practical realization of these advancements is hampered by the challenges of fabricating large-area, defect-free membranes containing a high density of open, small diameter SWCNT pores. Here, large-scale (≈60 cm2) nanocomposite membranes comprising of an ultrahigh density (1.89 × 1012 tubes cm-2) of 1.7 nm SWCNTs as sole transport pathways are demonstrated. Complete opening of all conducting nanotubes in the composite enables unprecedented accuracy in quantifying the enhancement of pressure-driven transport for both gases (>290× Knudsen prediction) and liquids (6100× no-slip Hagen-Poiseuille prediction). Achieved water permeances (>200 L m-2 h-1 bar-1) greatly exceed those of state-of-the-art commercial nano- and ultrafiltration membranes of similar pore size. Fabricated membranes reject nanometer-sized molecules, permit fractionation of dyes from concentrated salt solutions, and exhibit excellent chemical resistance. Altogether, these SWCNT membranes offer new opportunities for energy-efficient nano- and ultrafiltration processes in chemically demanding environments.

Structural Anomalies and Electronic Properties of an Ionic Liquid under Nanoscale Confinement.

Ionic liquids (ILs) promise far greater electrochemical performance compared to aqueous systems, yet key physicochemical properties governing their assembly at interfaces within commonly used graphitic nanopores remain poorly understood. In this work, we combine synchrotron X-ray scattering with first-principles molecular dynamics simulations to unravel key structural characteristics of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([TFSI]-) ionic liquids confined in carbon slit pores. X-ray scattering reveals selective pore filling due to size exclusion, while filled pores exhibit disruption in the IL intermolecular structure, the extent of which increases for narrower slit pores. First-principles simulations corroborate this finding and quantitatively describe how perturbations in the local IL structure, particularly the hydrogen-bond network, depend strongly on the degree of confinement. Despite significant deviations in structure under confinement, electrochemical stability remains intact, which is important for energy storage based on nanoporous carbon electrodes (e.g., supercapacitors).

Biomimetic potassium-selective nanopores.

Reproducing the exquisite ion selectivity displayed by biological ion channels in artificial nanopore systems has proven to be one of the most challenging tasks undertaken by the nanopore community, yet a successful achievement of this goal offers immense technological potential. Here, we show a strategy to design solid-state nanopores that selectively transport potassium ions and show negligible conductance for sodium ions. The nanopores contain walls decorated with 4'-aminobenzo-18-crown-6 ether and single-stranded DNA (ssDNA) molecules located at one pore entrance. The ionic selectivity stems from facilitated transport of potassium ions in the pore region containing crown ether, while the highly charged ssDNA plays the role of a cation filter. Achieving potassium selectivity in solid-state nanopores opens new avenues toward advanced separation processes, more efficient biosensing technologies, and novel biomimetic nanopore systems.

Carbon Nanotubes and Related Nanomaterials: Critical Advances and Challenges for Synthesis toward Mainstream Commercial Applications.

Advances in the synthesis and scalable manufacturing of single-walled carbon nanotubes (SWCNTs) remain critical to realizing many important commercial applications. Here we review recent breakthroughs in the synthesis of SWCNTs and highlight key ongoing research areas and challenges. A few key applications that capitalize on the properties of SWCNTs are also reviewed with respect to the recent synthesis breakthroughs and ways in which synthesis science can enable advances in these applications. While the primary focus of this review is on the science framework of SWCNT growth, we draw connections to mechanisms underlying the synthesis of other 1D and 2D materials such as boron nitride nanotubes and graphene.

Effect of Enhanced Thermal Stability of Alumina Support Layer on Growth of Vertically Aligned Single-Walled Carbon Nanotubes and Their Application in Nanofiltration Membranes.

We investigate the thermal stability of alumina supporting layers sputtered at different conditions and its effect on the growth of aligned single-walled carbon nanotube arrays. Radio frequency magnetron sputtering of alumina under oxygen-argon atmosphere produces a Si-rich alumina alloy film on a silicon substrate. Atomic force microscopy on the annealed catalysts reveals that Si-rich alumina films are more stable than alumina layers with low Si content at the elevated temperatures at which the growth of single-walled carbon nanotubes is initiated. The enhanced thermal stability of the Si-rich alumina layer results in a narrower (< 2.2 nm) diameter distribution of the single-walled carbon nanotubes. Thanks to the smaller diameters of their nanotube pores, membranes fabricated with vertically aligned nanotubes grown on the stable layers display improved ion selectivity.

Quantifying the Hierarchical Order in Self-Aligned Carbon Nanotubes from Atomic to Micrometer Scale.

Fundamental understanding of structure-property relationships in hierarchically organized nanostructures is crucial for the development of new functionality, yet quantifying structure across multiple length scales is challenging. In this work, we used nondestructive X-ray scattering to quantitatively map the multiscale structure of hierarchically self-organized carbon nanotube (CNT) "forests" across 4 orders of magnitude in length scale, from 2.0 Å to 1.5 µm. Fully resolved structural features include the graphitic honeycomb lattice and interlayer walls (atomic), CNT diameter (nano), as well as the greater CNT ensemble (meso) and large corrugations (micro). Correlating orientational order across hierarchical levels revealed a cascading decrease as we probed finer structural feature sizes with enhanced sensitivity to small-scale disorder. Furthermore, we established qualitative relationships for single-, few-, and multiwall CNT forest characteristics, showing that multiscale orientational order is directly correlated with number density spanning 109-1012 cm-2, yet order is inversely proportional to CNT diameter, number of walls, and atomic defects. Lastly, we captured and quantified ultralow-q meridional scattering features and built a phenomenological model of the large-scale CNT forest morphology, which predicted and confirmed that these features arise due to microscale corrugations along the vertical forest direction. Providing detailed structural information at multiple length scales is important for design and synthesis of CNT materials as well as other hierarchically organized nanostructures.

Carbon Nanotubes: Ultrabreathable and Protective Membranes with Sub-5 nm Carbon Nanotube Pores (Adv. Mater. 28/2016).

A flexible membrane with sub-5 nm single-walled carbon nanotube (SWNT) pores is developed by F. Fornasiero and co-workers, as described on page 5871, for application as a key component of protective, yet breathable fabrics. The SWNTs are shown to enable exceptionally fast transport of water vapor under a concentration driving force. Thus, membranes having SWNTs as moisture-conductive pores feature outstanding breathability and provide a high degree of protection from biological threats by size exclusion.

Ultrabreathable and Protective Membranes with Sub-5 nm Carbon Nanotube Pores.

Small-diameter carbon nanotubes (CNTs) are shown to enable exceptionally fast transport of water vapor under a concentration gradient driving force. Thanks to this property, membranes having sub-5 nm CNTs as conductive pores feature outstanding breathability while maintaining a high degree of protection from biothreats by size exclusion.

Nanofluidic Transport through Isolated Carbon Nanotube Channels: Advances, Controversies, and Challenges.

Owing to their simple chemistry and structure, controllable geometry, and a plethora of unusual yet exciting transport properties, carbon nanotubes (CNTs) have emerged as exceptional channels for fundamental nanofluidic studies, as well as building blocks for future fluidic devices that can outperform current technology in many applications. Leveraging the unique fluidic properties of CNTs in advanced systems requires a full understanding of their physical origin. Recent advancements in nanofabrication technology enable nanofluidic devices to be built with a single, nanometer-wide CNT as a fluidic pathway. These novel platforms with isolated CNT nanochannels offer distinct advantages for establishing quantitative structure-transport correlations in comparison with membranes containing many CNT pores. In addition, they are promising components for single-molecule sensors as well as for building nanotube-based circuits wherein fluidics and electronics can be coupled. With such advanced device architecture, molecular and ionic transport can be manipulated with vastly enhanced control for applications in sensing, separation, detection, and therapeutic delivery. Recent achievements in fabricating isolated-CNT nanofluidic platforms are highlighted, along with the most-significant findings each platform enables for water, ion, and molecular transport. The implications of these findings and remaining open questions on the exceptional fluidic properties of CNTs are also discussed.

Laser-assisted simultaneous transfer and patterning of vertically aligned carbon nanotube arrays on polymer substrates for flexible devices.

We demonstrate a laser-assisted dry transfer technique for assembling patterns of vertically aligned carbon nanotube arrays on a flexible polymeric substrate. A laser beam is applied to the interface of a nanotube array and a polycarbonate sheet in contact with one another. The absorbed laser heat promotes nanotube adhesion to the polymer in the irradiated regions and enables selective pattern transfer. A combination of the thermal transfer mechanism with rapid direct writing capability of focused laser beam irradiation allows us to achieve simultaneous material transfer and direct micropatterning in a single processing step. Furthermore, we demonstrate that malleability of the nanotube arrays transferred onto a flexible substrate enables post-transfer tailoring of electric conductance by collapsing the aligned nanotubes in different directions. This work suggests that the laser-assisted transfer technique provides an efficient route to using vertically aligned nanotubes as conductive elements in flexible device applications.

pH-tunable ion selectivity in carbon nanotube pores.

The selectivity of ion transport in nanochannels is of primary importance for a number of physical, chemical, and biological processes ranging from fluid separation to ion-channel-regulated cellular processes. Fundamental understanding of these phenomena requires model nanochannels with well-defined and controllable structural properties. Carbon nanotubes provide an ideal choice for nanofluidic studies because of their simple chemistry and structure, the atomic scale smoothness and chemical inertness of the graphitic walls, and the tunability of their diameter and length. Here, we investigate the selectivity of single and, for the first time, binary salt mixtures transport through narrow carbon nanotubes that act as the only pores in a silicon nitride membrane. We demonstrate that negatively charged carboxylic groups are responsible for the ion rejection performance of carbon nanotube pores and that ion permeation of small salts can be tuned by varying solution pH. Investigation of the effect of solution composition and ion valences for binary electrolytes with common cation in a pressure-driven flow reveals that the addition of slower diffusing multivalent anions to a solution of faster diffusing monovalent anions favors permeation of the monovalent anion. Larger fractions and valences of the added multivalent anions lower the rejection of the monovalent anion. In some cases, we observe negative rejection at low monovalent ion content.