Understanding the behavior of gas within confined ionic liquids (ILs) is important for a wide range of emerging energy, separation, and sensing technologies. However, the mechanisms governing gas solubility and molecular structure within these systems remain largely unknown. Here, we investigate the factors that dictate the intercalation and arrangement of CO2, N2 and O2, in a commonly used IL (1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM+][PF6-]) confined within neutral and charged 2.1 nm diameter carbon nanotubes (CNTs) via molecular dynamics simulations and enhanced free energy sampling methods. Our simulations show that the gas selectivity in these systems can be explained by a competitive complex interplay between confinement, charge state of CNTs, and IL properties. We then experimentally validate a subset of these predictions using a novel device consisting of electrically addressable, IL-infilled CNTs which we expose to CO2 and O2 in a N2 background. Our findings help to disentangle the relative importance of tuning gas solubility and preferential proximity to the CNT wall for maximizing measurable changes of electrochemical signals. These insights provide a foundation for engineering future electrochemical systems utilized in gas sensing or separation applications.

The advent of ultrabright fourth generation X-ray light sources, including X-ray free-electron lasers (XFELs) and diffraction limited synchrotrons, has significantly advanced the field of serial macromolecular protein crystallography (SX). SX experiments demand a continuous supply of fresh microcrystalline sample, ideally while minimizing overall sample consumption. Here, we introduce a novel, robust, and user-friendly polymer film technology that can be assembled in various configurations to encapsulate protein microcrystals and provide sample support for SX. This system provides an efficient hydration barrier over extended durations while maintaining an exceptionally low X-ray background. We have validated this technology by assessing hydration retention under both ambient and ultra-high vacuum conditions, and by evaluating its mechanical stability under XFEL pulses. Furthermore, we have demonstrated the effectiveness of this approach in two room-temperature serial crystallography studies to determine the structure of a 24 kDa Rapid Encystment Phenotype (REP24) protein from Franciscella tularensis.

The efficient measurement of the length distribution of nanotubes, nanowires, and other one-dimensional (1D) nanoparticles in solution is important to enable their incorporation into materials and devices and to optimize their processing for properties of interest, such as thermal/electrical conductivity or mechanical strength, in suspensions and composites. We report an electric-field (E-field)-assisted optical-polarimetry technique to measure the length distribution of ensembles of high-aspect-ratio particles in dilute suspension. The degree of alignment of polarizable 1D particles suspended in a fluid under Brownian motion explicitly depends on the E-field strength and the particle length. We show that it is possible to extract the length distribution of 1D nanoparticles suspended in an insulating fluid by applying a range of E-fields and using optical polarimetry to measure the corresponding alignment order parameter. Notably, the method is relatively insensitive to the diameter of the 1D particles, which can be poorly known or vary within a sample. The technique is validated with silver nanowires and carbon nanotubes of known lengths, as well as polymer-depletion-length-separated single-wall carbon nanotube samples with length distributions independently measured with analytical ultracentrifugation. Finally, we demonstrate the ability of the optical-polarimetry technique to quantify changes in the length distribution of ultranarrow, sub-nanometer-diameter single-wall carbon nanotubes under different types and durations of ultrasonication. Within its range of applicability (polarizable 1D nanoparticles in the 0.5 to 15 μm length range, constrained by the voltage stability of the media and the suspended particles), the E-field-assisted optical-polarimetry method is a particularly efficient and accurate method to measure the length distribution of nanowires and nanotubes in suspension.

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.

Current Lithium-ion batteries (LIBs) are limited to energy densities of ~150 Wh/kg and pose safety issues associated with dendrite formation and the use of flammable liquid electrolytes that can result in the common battery failure known as thermal runaway and explosion. Lithium metal is an ideal anode for high energy density LIBs due to its high theoretical capacity (3860 mAh/g) but is dangerous due to its propensity to form dendrites. Carbon nanotubes (CNTs) with superior electronic, mechanical, and structural properties provide an exciting alternative as anode for high energy density LIBs. LIBs with vertically aligned CNTs forest help achieve the capacity retention > 80% and superior efficiency over 1000 charging-discharging cycles. However, a fundamental understanding of Li+ ion storage within CNT anodes is largely unexplored and lacking. Experimental characterization of Li+ ion storage in CNT anodes is expensive and challenging. Previous theoretical studies have evaluated storage mechanism for isolated Li+ ions within small diameter CNTs (< 1.5 nm) forest. In common organic liquid electrolytes, Li+ ions prefer to be solvated and therefore isolated Li+ ions cannot accurately describe the Li+ storage mechanism especially in large diameter CNTs. In the current study, we carefully investigated the de-solvation mechanisms for Li+ ions in EC: EMC (3/7 w/w) 1.2 M LiPF6 liquid electrolytes both inside and outside of pristine CNT. The calculated de-solvation energies for Li+ ion adsorption onto the outside surface (~0.4-0.5 eV) of CNTs show relatively lower energies as compared to inside surface (~ 0.9-1.0 eV) of CNTs. We therefore claim that the Li+ ion storage strongly occurs on the outside surface of pristine defect-free CNTs. We further employ classical molecular dynamics simulations to investigate the Li+ ion storage on the outside of CNTs. The classical molecular dynamics simulations reveal a capacitive-type storage mechanism for pristine CNTs forest. Recent experimental reports suggest a large fraction of storage mechanism in CNT anode to be capacitive type (> 55 %) which supports the findings from atomistic modeling. Introducing structural defects (n-membered C-C rings), functional groups (-OH, =O, -COOH) etc... can lead to intercalation or plating-type Li ion storage in CNT forest which would result in higher capacity as well as energy density. However, for pristine CNTs we report the Li+ ion storage mechanism to be purely capacitive and therefore would serve as potential supercapacitor rather than battery. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

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.

Nanotechnology offers a variety of new tools for the design of next-generation personal protective equipment (PPE). One example is the use of two-dimensional materials as coatings that enhance the performance and ergonomics of elastomeric gloves designed to protect users from hazardous chemicals. Desirable features in such coatings may include molecular barrier function, liquid droplet repellency, stretchability for compatibility with the elastomer, breathability, and an ultrathin profile that preserves the user's manual dexterity and tactile sensation. The present work explores the potential of engineered graphene-based films with out-of-plane texturing as a novel platform to meet these multifold requirements. Graphene-based films in different formulations were fabricated from water-borne inks by vacuum filtration and solution casting methods on glove-derived nitrile rubber substrates. The various coatings were then subjected to tests of molecular permeation by model volatile organic compounds, droplet contact angle, breathability, and mechanical stability during stretching and solvent immersion. The films dramatically improve the barrier properties of glove-derived nitrile. The out-of-plane graphene texturing imparts stretchability through microscale folding/unfolding, while also enhancing droplet repellency in some cases through a lotus-like roughening effect. The combined results suggest that engineered textured graphene-based films are a promising platform for creating multifunctional coatings for a next generation of chemically protective gloves and other elastomer-based PPE.

Conventional dialyzer membranes typically comprise of unevenly distributed polydisperse, tortuous, rough pores, embedded in relatively thick approximate to 20-50 mu m polymer layers wherein separation occurs via size exclusion as well as differences in diffusivity of the permeating species. However, transport in such polymeric pores is increasingly hindered as the molecule size approaches the pore dimension, resulting in significant retention of undesirable middle molecules (>= 15-60 kDa) and uremic toxins. Enhanced removal of middle molecules is usually accompanied by high albumin loss (approximate to 66 kDa) causing hypoalbuminemia. Here, the scalable bottom-up fabrication of wafer-scale carbon nanotube (CNT) membranes with highly aligned, low-friction, straight-channels/capillaries and narrow pore-diameter distributions (approximate to 0.5-4.5 nm) is demonstrated, to overcome persistent challenges in hemofiltration/hemodialysis. Using fluorescein isothiocyanate (FITC)-Ficoll 70 and albumin in phosphate buffered saline (PBS) as well as in bovine blood plasma, it is shown that CNT membranes can allow for significantly higher hydraulic permeability (more than an order of magnitude when normalized to pore area) than commercial high-flux hemofiltration/hemodialysis membranes (HF 400), as well as greatly enhance removal of middle molecules while maintaining comparable albumin retention. These findings are rationalized via an N-pore transport model that highlights the critical role of molecular flexing and deformation during size-selective transport within nanoscale confinements of the CNTs. The unique transport characteristics of CNTs coupled with size-exclusion and wafer-scale fabrication offer transformative advances for hemofiltration, and the obtained insight into molecular transport can aid advancements in several other bio-systems/applications beyond hemofiltration/hemodialysis.

Robust synthesis of vertically aligned carbon nanotubes (VACNT) at large scale is required to accelerate deployment of numerous cutting-edge devices to emerging commercial applications.1 Large-area single-walled (SW) CNT forests with high densities and small diameters are especially important for many applications, yet they are conspicuously absent from the literature due to reproducibility and synthesis challenges, which are further exacerbated when flexible metal foils are used as support instead of traditional Si or quartz wafers. To address this need, we demonstrate that the structural characteristics of SWCNTs produced in a growth regime dominated by bulk diffusion of the gaseous carbon precursor are remarkably invariant over a broad range of process conditions (precursor concentration increased up to 30-fold, catalyst substrate area from 1 cm2 to 180 cm2, growth pressure from 20 to 790 mbar, and gas flowrates up to 8-fold).2 Forests structural properties are also preserved when growth is transitioned from Si wafers to Inconel metal foils.3 We show that a simple growth kinetics model that accounts for both reactant bulk diffusion and competing byproduct formation in the presence of excess hydrogen quantitatively reproduces the experimental data in the entire isothermal parameter space. The model enables critical predictions for process scale-up optimization including a potential 6-fold increase in CNT production rate, a ~ 90% carbon conversion efficiency in select conditions, and elimination of reaction rate decay observed at high pressures by using a hydrogen-free growth environment. This model-guided opportunity to substantially improve synthesis throughput and efficiency, in conjunction with the remarkably invariant CNT properties on both metal and insulating substrates, is appealing for reliable VACNT device fabrication at both small and industrial scales. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. References Rao, R.; Pint, C. L.; Islam, A. E.; Weatherup, R. S.; Hofmann, S.; Meshot, E. R.; Wu, F.; Zhou, C.; Dee, N.; Amama, P. B.; Carpena-Nuñez, J.; Shi, W.; Plata, D. L.; Penev, E. S.; Yakobson, B. I.; Balbuena, P. B.; Bichara, C.; Futaba, D. N.; Noda, S.; Shin, H.; Kim, K. S.; Simard, B.; Mirri, F.; Pasquali, M.; Fornasiero, F.; Kauppinen, E. I.; Arnold, M.; Cola, B. A.; Nikolaev, P.; Arepalli, S.; Cheng, H.-M.; Zakharov, D. N.; Stach, E. A.; Zhang, J.; Wei, F.; Terrones, M.; Geohegan, D. B.; Maruyama, B.; Maruyama, S.; Li, Y.; Adams, W. W.; Hart, A. J. Carbon Nanotubes and Related Nanomaterials: Critical Advances and Challenges for Synthesis toward Mainstream Commercial Applications. ACS Nano 2018, 12, 11756-11784. Park, S. J.; Moyer-Vanderburgh, K.; Buchsbaum, S. F.; Meshot, E. R.; Jue, M. L.; Wu, K. J.; Fornasiero, F. Synthesis of wafer-scale SWCNT forests with remarkably invariant structural properties in a bulk-diffusion-controlled kinetic regime. Carbon 2023, 201, 745-755. Moyer-Vanderburgh, K.; Ma, M. C.; Park, S. J.; Jue, M. L.; Buchsbaum, S. F.; Wu, K. J.; Wood, M.; Ye, J.; Fornasiero, F. Growth and Performance of High-Quality SWCNT Forests on Inconel Foils as Lithium-Ion Battery Anodes. ACS Appl Mater Interfaces 2022, 14, 54981-54991.

Synthetic materials designed to enable rapid and finely tuned diffusion through semi-permeable nano and microscale pores have generally fallen short when compared to their biological counterparts. As a result, applications such as hemodialysis, drug delivery, and biomolecule purifications often require extensive run times and produce imperfect permeate solutions. Towards bridging this gap, we have recently demonstrated that, under a concentration gradient, a wide range of ions diffuse through atomically smooth carbon nanotube pores at rates more than an order of magnitude above those seen in bulk. This observation comes in a pore/molecule size regime where hindered diffusion was previously thought to apply. Here, we extend these results to include more complex and biologically relevant molecules and study how transport rates driven by diffusion depend on molecular properties such as size and flexibility. Further, we work to understand how the unique nanofluidic phenomena occurring in our pores may enable improved performance in dialysis applications by impacting selectivity, permeability, and molecular cutoff profiles. These results help to shed light on mechanisms governing diffusive transport in certain nanoscale pores that remain only partially understood and bring us closer to harnessing them in future separation technologies.

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.

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.

Owing to their remarkable properties and ordered architecture, vertically aligned CNT forests (VACNT) hold promises for countless applications ranging from energy storage to multifunctional fiber production. Over the last three decades, studies of carbon nanotube (CNT) growth have provided invaluable insight into the CNT nucleation and growth mechanism and enabled critical advancements in nanotechnology. Nevertheless, the ability to fully harness the exceptional VACNT properties in commercial devices is bottlenecked by compatibility of current CNT synthesis processes with large-scale manufacturing. Metal foil substrates present an economic alternative to traditional insulating substrates, like silicon or quartz, and are compatible with both roll-to-roll and automated, large-scale, batch processes. Compared to CNT growth on Si substrates, metal foils present additional challenges, such as increased roughness and reactivity at high temperatures. Nonetheless, many successful VACNT growths on conducting metal foils have been reported, which demonstrate the feasibility of metal substrate use for large-volume production of high-quality CNTs. In this review, we discuss advancements in the field of VACNT growth on metal foil and specifically examine different choices for metal substrates, barrier and catalyst layers, deposition and growth methods, resulting CNT characteristics, and highlight a number of applications that benefit from CNT growth on metal substrates and transition to large-scale manufacturing.

Surface-tethered polymers have important applications in functional polymer coatings, particularly for the development of chemically responsive surfaces. Here, we combined the traditional grafting-to and grafting-from methods to create a new surface grafting strategy, termed grafting-to and from, using surface-initiated ring-opening metathesis polymerization (SI-ROMP). In this method, poly(pentafluorophenyl methacrylate) is grafted to an amine terminated surface. Surplus reactive esters after reaction with surface amines render this polymer a connecting or tie layer that can be further reacted to provide dense ROMP initiation sites. This amplification of grafting sites results in thick and environmentally stable polymer brushes upon SIROMP. With the goal of developing polymer-grafted breathable membranes that autonomously react to multiple chemical warfare agents (CWAs), we demonstrate the benefit of this method by employing amine reactive monomers in the grafting-from step. This enables diverse postsynthetic functionalization for the facile screening of chemical motifs to enhance response capabilities to mustard blister agents. Surface-tethered triarylmethanol-containing polymers with four distinct functional groups are prepared and challenged with the vapor of 2-chloroethyl ethyl sulfide (CEES), a simulant of mustard agent, in humid air. Importantly, hydroxyl groups effectively improve CWA response and the resulting polymer brushes show chain collapse after both CEES and diethylchlorophosphate (DCP) treatment. Our results illustrate that the grafting-to and from method can be used to grow functional and robust polymer coatings for various applications.

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.

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.

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 × 10 4 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.