Single-walled Carbon Nanotube Membranes Research Articles

Birefringent optical responses of single-chirality carbon nanotube membranes

Membranes composed of single-walled carbon nanotubes (SWCNTs) with a specific chiral structure (chirality) possess unique optical properties dominated by thermally robust quasi-one-dimensional excitons. Therefore they have emerged as promising materials for photonic and/or thermo-optic applications. As SWCNTs in the membranes are usually aligned two-dimensionally in a plane, and the optical responses of individual SWCNTs are highly anisotropic, the macroscopic responses of membranes are expected to depend on the light-propagation direction. However, the complex refractive-index spectra of some membrane axes are unknown, hindering the optical design of SWCNT-based devices that respond to arbitrarily propagating light. Here, we report the anisotropic complex refractive index spectra of a single-chirality SWCNT membrane fabricated via vacuum filtration. The polarization- and angle-resolved reflection spectra were obtained in the near-infrared-to-visible region. All spectral features in different polarizations and incident angle configurations were consistent with a uniaxial birefringent membrane, reflecting the random in-plane orientations of the SWCNTs. The ordinary (in-plane) refractive index spectra presented a series of sharp resonances of parallel-polarized excitons. The extraordinary (out-of-plane) refractive index in the 0.8–2.4 eV range was determined as ∼1.9. The extraordinary spectra included small but indispensable contributions from the cross-polarized exciton resonance, which are necessary for properly predicting the angle-dependent optical responses of the membrane. By completely unveiling the birefringent optical responses of single-chirality SWCNT membranes, this work paves the way for integrating SWNCT membranes into precise and diverse photonic and/or thermo-optic devices.

(Invited) Bio-Applications of Carbon Nanotubes for NIR Imaging Probes and Guided Bone Regeneration Membranes

Single-walled carbon nanotubes (CNTs) have been expected for biological and medical applications because of their unique optical and chemical properties. One of the promising applications is imaging probes because CNTs show fluorescence in the near-infrared (NIR) region, which is highly transparent for biomaterials. We have reported the synthesis method of the epoxide-type oxygen-doped CNTs (Ep-CNTs) and their application as a near-infrared fluorescent probe [1-3]. Treated (6, 5) nanotubes show photoluminescence at ~1280 nm, which corresponds to the most transparent regions for biomaterials [1]. Immunoassay and fluorescence vascular angiography of mice were demonstrated by using the produced Ep-CNTs as infrared fluorescent labels [1,3] and imaging agents [1,2], respectively. From a practical point of view, the biodistributions of the Ep-CNTs imaging probe after administration to mice were investigated in detail [2]. In addition, the biological responses of mice following administration, which are relevant to safety, were also introduced [2].More recently, we found that CNTs exhibit high compatibility with bone tissue [4]. The guided bone regeneration (GBR) technique is commonly applied to reconstruct alveolar bone and treat peri-implant bone defects. It was found that CNT-based membrane for GBR exhibits high strength to provide a space for bone formation and provide cellular shielding to induce osteogenesis.In this meeting, we will report above biological and medical applications of CNTs in detail.1. Y. Iizumi, M. Yudasaka, J. Kim, H. Sakakita, T. Takeuchi, T. Okazaki, Oxygen-doped carbon nanotubes for near-infrared fluorescent labels and imaging probes, Sci. Rep., 8, 6272 (2018).2. T. Takeuchi, Y. Iizumi, M. Yudasaka, S. K. Kondoh, T. Okazaki, Characterization and biodistribution analysis of oxygen-doped single-walled carbon nanotubes used as in vivo fluorescence imaging probes, Bioconjugate Chem., 30, 1323−1330 (2019). (Cover Article)3. K. Kojima, Y. Iizumi, M. Zhang, T. Okazaki, Streptavidin-conjugated oxygen-doped single-walled carbon nanotubes as near-infrared labels for immunoassays, Langmuir, 38, 1509-1513 (2022).4. Y. Xu, E. Hirata, Y. Iizumi, N. Ushijima, K. Kubota, S. Kimura, Y. Maeda, T. Okazaki, A. Yokoyama, Single-walled Carbon Nanotube Membranes Accelerate Active Osteogenesis in Bone Defects: Potential of Guided Bone Regeneration Membranes, ACS Biomater. Sci. Eng., 8, 1667-1675 (2022).

Electrochemical assembly of single-walled carbon nanotube/polypyrrole/tellurium/lead telluride multi-layer nanocomposite films for room-temperature flexible thermoelectric application

With the complexity and diversification of thermoelectric (TE) application scenarios, it becomes increasingly difficult for single-component thermoelectric materials to satisfy practical demands. Therefore, recent researches have largely focused on the development of the multi-component nanocomposites, which are probably a good solution for the TE application of some materials that are not eligible when used alone. In this work, a seires of single-walled carbon nanotube (SWCNT)/polypyrrole (PPy)/tellurium (Te)/lead telluride (PbTe) multi-layer flexible composite films were fabricated via the successive electrodeposition of the flexible PPy layer with a low thermal conductivity, the ultra-thin Te induction layer, and the brittle PbTe layer with a large Seebeck coefficient over the pre-fabricated SWCNT membrane electrode with a high electrical conductivity. Through the complementary advantages between different components and the multiple synergies of the interface engineering, the SWCNT/PPy/Te/PbTe composites harvested the excellent TE performance with a maximum power factor (PF) of 929.8 ± 35.4 µW m−1 K−2 at room temperature, outperforming those of most of the electrochemically-prepared organic/inorganic TE composites reported previously. This work evidenced that the electrochemical multi-layer assembly is a feasible tactic for constructing special thermoelectric materials to meet customized requirements, which could also be applied to other material platforms.

Low-pressure carbon nanotube membrane with different surface properties for the removal of organic dyes and PPCPs

Low-pressure carbon nanotube membranes (CNT membranes) was prepared with multi-walled carbon nanotubes (MWCNTs), carboxyl functionalized MWCNTs (COOH-MWCNTs) and single-walled carbon nanotubes (SWCNTs). Surface properties of MWCNTs and SWCNTs were further altered by their non-covalent functionalization with Humic acid (HA), Sodium dodecyl sulfate (SDS), Sodium alginate (SA) and Polyethylene glycol (PEG). The CNT membranes with different surface properties were then used for the removal of organic dyes and pharmaceuticals and personal care products (PPCPs). The results revealed that HA/SDS/SA non-covalent functionalized MWCNTs membrane significantly promoted the removal of cationic dye MB, while it slightly interfered the removal of anionic dye RB19. During the dynamic filtration process, a 20∼30% increase of MB removal was promoted by HA/SDS/SA-MWCNTs membrane compared with the MWCNTs membrane, while the HA/SDS/SA-MWCNTs membrane significantly deteriorated the removal of PPCPs. The specific surface area of CNTs played a very important role in the dynamic filtration process of CNT membranes. The removal rate of PPCPs by SWCNTs membranes was almost all above 70% after 120 min’s filtration, and a further 10% increase was promoted by SA-SWCNTs membrane. HA and SDS non-covalent functionalization only slightly deteriorate the removal of PPCPs, and the removal rate of majority of PPCPs by HA-SWCNTs membrane and SDS-SWCNTs membrane remained over 60% and 30%. This work present new insight for the effectiveness of low-pressure CNT membranes in actual application, where the impact of competitive background organic materials on the removal of Low-MW organic pollutants were sometimes overestimated.

Ar permeability through densified single-walled carbon nanotube-based membranes

Single-walled carbon nanotube (SWCNT)-based membranes (pellicles) and gas counterflows are used as a debris mitigation system in extreme ultraviolet (EUV) lithography. Densification with volatile liquids is a well-known approach to tune the performance of SWCNT membranes. However, densification can change the gas permeability through SWCNT membranes, violating the circulation of buffer gas counterflows. In the present work, we investigate the Ar permeability through SWCNT membranes before and after densification with isopropyl alcohol in the pressure drop test. The effective diffusivity of Ar through pristine and densified SWCNT membranes is, respectively, calculated to be Deffpristine = 330 × 109 m2 s−1 and Deffdensified = 4 × 109 m2 s−1. We developed a probabilistic model of gas penetration through SWCNT membranes. On the basis of the experimental data, the probabilities of Ar atoms penetrating through pristine and densified SWCNT membranes are estimated to be 8% and 0.1%, respectively. Structural changes in SWCNT membranes after densification with scanning electron microscopy and the Brunauer–Emmett–Teller technique are demonstrated. The bulk density of SWCNT membranes, measured using x-ray reflectometry, is found to be 0.38 and 0.89 g/cm3 before and after densification, respectively. The temporal dynamic of isopropyl alcohol evaporation from the volume of SWCNT membranes is analyzed using Fourier-transform infrared spectroscopy (FTIR). Results obtained using EUV and FTIR spectroscopy show that isopropyl alcohol is present in the volume of the SWCNT membrane even after the membrane has been left in vacuum (P < 0.01 Pa) for 22 h.

InSn plasma penetration through protective single-walled carbon nanotube-based membranes

Laser-produced plasma sources of short-wavelength (1–20-nm) radiation are actively used nowadays in numerous applications, including water-window microscopy and extreme ultra-violet lithography. Suppression of laser-plasma debris (responsible for damaging optics) is crucial for the lifetime prolongation of optical systems operated with the short-wavelength radiation. Here, we examine the capability of single-walled carbon nanotube (SWCNT)-based membranes to decrease an InSn plasma flux containing both ions and atoms. Faraday cup measurements show that 40- and 90-nm-thick SWCNT membranes reduce the total charge transition by 20 and 130 times, respectively. The ion analyzer measurements demonstrate that ions pass through the membrane mainly due to the collisionless (ballistic) mechanism. Using scanning electron microscopy, we estimate a decrease in a plasma (ions + atoms) flux to be of 18 and 140 times for 40- and 90-nm-thick SWCNT-based membranes, respectively. The average plasma flux attenuation coefficient of SWCNT membranes is calculated as k = 0.063 nm−1.

Renewable single-walled carbon nanotube membranes for extreme ultraviolet pellicle applications

We propose a facile, cost-efficient, environmentally friendly, and scalable process to renew single-walled carbon nanotube membranes serving as extreme ultraviolet (EUV) protective pellicles. The method comprises of high-temperature treatment of the membrane by Joule (resistive) heating at temperatures higher than 1000 °C and pressure below 0.3 Pa. Using model Sn aerosol nanoparticles, the primary contaminant from extreme ultraviolet light sources, we demonstrate the proposed method to clean the membrane with the power consumption as low as 20 W/cm2. We show the proposed method to cause no harm to carbon nanotube structure, opening a route towards multiple membrane renovation. We confirm the applicability of the approach using in situ deposition from the semi-industrial EUV light source and subsequent Sn-based contaminant removal, which restores the EUV-UV-vis-NIR transmittance of the film and, therefore, the light source performance. The proposed method supports pulse-cycling opening an avenue for enhanced protection of the lithography mask and stable performance of the EUV light source. Additionally, the approach suits other composite contaminants based on such species as Pb, In, Sb, etc.

Single-Walled Carbon Nanotube Membranes Accelerate Active Osteogenesis in Bone Defects: Potential of Guided Bone Regeneration Membranes.

Carbon nanotubes (CNTs) are potentially important biomaterials because of their chemical, physical, and biological properties. Our research indicates that CNTs exhibit high compatibility with bone tissue. The guided bone regeneration (GBR) technique is commonly applied to reconstruct alveolar bone and treat peri-implant bone defects. In GBR, bone defects are covered with a barrier membrane to prevent the entry of nonosteogenic cells such as epithelial cells and fibroblasts. The barrier membrane also maintains a space for new bone formation. However, the mechanical and biological properties of materials previously used in clinical practice sometimes delayed bone regeneration. In this study, we developed a CNT-based membrane for GBR exhibiting high strength to provide a space for bone formation and provide cellular shielding to induce osteogenesis. The CNT membrane was made via the dispersion of single-walled CNTs (SWCNTs) in hyaluronic acid solution followed by filtration. The CNT membrane assumed a nanostructure surface due to the bundled SWCNTs and exhibited high strength and hydrophilicity after oxidation. In addition, the membrane promoted the proliferation of osteoblasts but not nonosteogenic cells. CNT membranes were used to cover experimental bone defects made in rat calvaria. At 8 weeks after surgery, more extensive bone formation was observed in membrane-covered defects compared with bone defects not covered with membrane. Almost no diffusion of CNTs was observed around the membrane. These results indicate that the CNT membrane has adequate strength, stability, and surface characteristics for osteoblasts, and its shielding properties promote bone formation. Demonstration of the safety and osteogenic potential of the CNT membranes through further animal studies should facilitate their clinical application in GBR.

Penetration of liquid metal droplets through membranes based on single-wall carbon nanotubes

The probability of penetration of droplets with different sizes (20 nm ~ 1 μm) through a thin (~ 90 nm) protective membrane based on single-walled carbon nanotubes (SWCNT) has been experimentally determined. It is shown that the probability of penetration of droplets less than 200 nm in size through the SWCNT membrane is 0.4%. The paper presents the results of comparing the droplets deposition rate in terms of "effective" thickness measured in the experiments and calculated via the RZLINE model. The simulation results are in good agreement with the experimental data. Keywords: SWCNT membranes, droplet penetration, RZLINE code.

Modified Single-Walled Carbon Nanotube Membranes for the Elimination of Antibiotics from Water.

The hydrophilic and hydrophobic single-walled carbon nanotube membranes were prepared and progressively applied in sorption, filtration, and pertraction experiments with the aim of eliminating three antibiotics—tetracycline, sulfamethoxazole, and trimethoprim—as a single pollutant or as a mixture. The addition of SiO2 to the single-walled carbon nanotubes allowed a transparent study of the influence of porosity on the separation processes. The mild oxidation, increasing hydrophilicity, and reactivity of the single-walled carbon nanotube membranes with the pollutants were suitable for the filtration and sorption process, while non-oxidized materials with a hydrophobic layer were more appropriate for pertraction. The total pore volume increased with an increasing amount of SiO2 (from 743 to 1218 mm3/g) in the hydrophilic membranes. The hydrophobic layer completely covered the carbon nanotubes and SiO2 nanoparticles and provided significantly different membrane surface interactions with the antibiotics. Single-walled carbon nanotubes adsorbed the initial amount of antibiotics in less than 5 h. A time of 2.3 s was sufficient for the filtration of 98.8% of sulfamethoxazole, 95.5% of trimethoprim, and 87.0% of tetracycline. The thicker membranes demonstrate a higher adsorption capacity. However, the pertraction was slower than filtration, leading to total elimination of antibiotics (e.g., 3 days for tetracycline). The diffusion coefficient of the antibiotics varies between 0.7–2.7 × 10−10, depending on the addition of SiO2 in perfect agreement with the findings of the textural analysis and scanning electron microscopy observations. Similar to filtration, tetracycline is retained by the membranes more than sulfamethoxazole and trimethoprim.

Single-walled carbon nanotube membranes as non-reflective substrates for nanophotonic applications

We demonstrate that single-walled carbon nanotube (SWCNT) membranes can be successfully utilized as nanometer-thick substrates for enhanced visualization and facilitated study of individual nanoparticles. As model objects, we transfer optically resonant 200 nm silicon nanoparticles onto pristine and ethanol-densified SWCNT membranes by the femtosecond laser printing method. We image nanoparticles by scanning electron and bright-field optical microscopy, and characterize by linear and Raman scattering spectroscopy. The use of a pristine SWCNT membrane allows to achieve an order-of-magnitude enhancement of the optical contrast of the nanoparticle bright field image over the results shown in the case of the glass substrate use. The observed optical contrast enhancement is in agreement with the spectrophotometric measurements showing an extremely low specular reflectance of the pristine membrane (≤0.1%). Owing to the high transparency, negligibly small reflectance and thickness, SWCNT membranes offer a variety of perspective applications in nanophotonics, bioimaging and synchrotron radiation studies.

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.

Overcoming the Selectivity-Permeability Trade-Off with Nanoporous Carbon Nanotube Membranes

From energy storage to separation applications, performances of nanoporous membranes are typically limited by an inherent trade-off between transport rate and selectivity. For example, conventional protective garments sacrifice breathability to prevent exposure to harmful agents, and this trade-off severely hinders the duration of their active use. The discovery of enhanced fluid flow in single-walled carbon nanotubes (SWCNT) has provided a path toward combining the diametric properties of high selectivity and permeability into a single SWCNT-based material, yet successful demonstration of this promise remains elusive.Using as example the design of novel materials for protective clothing applications, herein we demonstrate a smart, nanoporous, SWCNT membrane that overcomes the limitation of conventional protective garments. Specifically, we show that the adoption of nanometer-wide SWCNTs for ultrafast moisture conduction [1] enables a simultaneous boost in size-sieving selectivity and water-vapor permeability by decreasing nanotube diameter, thereby overcoming the breathability/protection trade-off [2].Our membrane platform can rapidly and selectively transition from a highly breathable state in a safe environment to a protective state when exposed to a chemical threat. Dynamic response to chemical stimuli is achieved through the physical collapse of an ultrathin copolymer layer on the membrane surface, which efficiently gates transport through the SWCNT membrane pores [2].Multifunctional SWCNT membranes such these present exciting opportunities in many other areas including energy-efficient separations, energy storage, and smart delivery.

Single-walled carbon nanotube membranes for optical applications in the extreme ultraviolet range

In this paper, we explore the possibility of using free-standing thin films from single-walled carbon nanotube (SWCNT) material in optics of the extreme ultraviolet (EUV) range. Test samples were fabricated using an aerosol chemical vapor deposition method. Synchrotron radiation was used to record the transmittance spectra of samples in the EUV range. The measured transmittance for a film 40 nm thick almost monotonously increases from 76% at a wavelength of 20 nm–99% at a wavelength of 1 nm. The measured stress-strain curve for the test samples shows that the SWCNT-based thin films have rather high ductility as opposite to fragile films made of conventional solid state materials. We use numerical simulations to demonstrate that the film strain occurs mainly by straightening and sliding of the nanotubes past each other without forming of strain localization responsible for fragile behavior. The combination of high radiation transmittance and unique mechanical properties makes the SWCNT-based thin films very promising for use in the EUV optics. In particular, such films can be used to protect delicate optical elements for EUV lithography from their contamination with debris particles.

Carbon Nanotube-Based Membrane for Light-Driven, Simultaneous Proton and Electron Transport

Here we discuss the photon-driven transport of protons and electrons over hundreds of microns through a membrane based on vertically aligned single-walled carbon nanotubes (SWNTs). Electrons are photogenerated in colloidal CdSe quantum dots that have been noncovalently attached to the carbon nanotube membrane and can be delivered at potentials capable of reducing earth-abundant molecular catalysts that perform proton reduction. Proton transport is driven by the electron photocurrent and is shown to be faster through the SWNT-based membrane than through the commercial polymer Nafion. The potential utility of SWNT membranes for solar water splitting applications is demonstrated through their excellent proton and electron transport properties as well as their ability to interact with other components of water splitting systems, such as small-molecule electron acceptors.

Antimicrobial PVK:SWNT nanocomposite coated membrane for water purification: Performance and toxicity testing

This study demonstrated that coated nitrocellulose membranes with a nanocomposite containing 97% (wt%) of polyvinyl-N-carbazole (PVK) and 3% (wt%) of single-walled carbon nanotubes (SWNTs) (97:3 wt% ratio PVK:SWNT) achieve similar or improved removal of bacteria when compared with 100% SWNTs coated membranes. Membranes coated with the nanocomposite exhibited significant antimicrobial activity toward Gram-positive and Gram-negative bacteria (∼80–90%); and presented a virus removal efficiency of ∼2.5 logs. Bacterial cell membrane damage was considered a possible mechanism of cellular inactivation since higher efflux of intracellular material (Deoxyribonucleic acid, DNA) was quantified in the filtrate of PVK-SWNT and SWNT membranes than in the filtrate of control membranes. To evaluate possible application of these membrane filters for drinking water treatment, toxicity of PVK-SWNT was tested against fibroblast cells. The results demonstrated that PVK-SWNT was non toxic to fibroblast cells as opposed to pure SWNT (100%). These results suggest that it is possible to synthesize antimicrobial nitrocellulose membranes coated with SWNT based nanocomposites for drinking water treatment. Furthermore, membrane filters coated with the nanocomposite PVK-SWNT (97:3 wt% ratio PVK:SWNT) will produce more suitable coated membranes for drinking water than pure SWNTs coated membranes (100%), since the reduced load of SWNT in the nanocomposite will reduce the use of costly and toxic SWNT nanomaterial on the membranes.

Electrophoretically induced aqueous flow through single-walled carbon nanotube membranes

Electrophoresis, the motion of charged species through liquids and pores under an external electric field, has been principle source of chemical pumping for numerous micro- and nano-fluidic devices platforms. Recent studies of ion current through single or few carbon nanotube channels range from near bulk mobility to 2-7 orders of magnitude of enhancement but cannot directly measure ion flux. Membranes, with large number of nanotube pores, allow independent confirmation of ion current and flux. Here we report that the aqueous electrophoretic mobility of ions within the graphitic cores of carbon nanotube membranes, with a uniform pore size of 0.9 ± 0.2 nm, is enhanced ∼3 times that of bulk mobilities. The induced electroosmotic velocities are 4 orders of magnitude faster than those measured in conventional porous materials. We also show that a nanotube membrane can function as a rectifying diode due to ionic steric effects within tightly controlled nanotube diameter.

Ionic rectification by electrostatically actuated tethers on single walled carbon nanotube membranes

Large electrostatically actuating charged tethers (~2.5 nm) at the tip entrances of single walled carbon nanotubes (i.d. ~ 1.5 nm) can dramatically enhance ionic gating at the CNT core entrance. Significant rectification of small ions at physiological ionic strengths is observed and this system closely mimics the function of protein channels.

A nanosized Fe2O3 decorated single-walled carbon nanotube membrane as a high-performance flexible anode for lithium ion batteries

An Fe2O3/single-walled carbon nanotube (Fe2O3/SWCNT) membrane with high Fe2O3 loading (88.0 wt%) is prepared by oxidizing a flow-assembled Fe/SWCNT membrane. The Fe2O3/SWCNT membrane can be used as a flexible, binder-free and current-collector-free anode in lithium ion batteries, which shows a high reversible capacity of 1243 mA h g−1 at a current density of 50 mA g−1 and an excellent cyclic stability over 90 cycles at 500 mA g−1. The superior electrochemical performance of the Fe2O3/SWCNT electrode can be attributed to the structural characteristics of the SWCNT network and the uniformly distributed Fe2O3 nanoparticles (5–10 nm). The nanosized Fe2O3 has a short lithium ion diffusion length and minimal volume change during lithiation–delithiation. The high loading ratio of Fe2O3 nanoparticles renders the high capacity. The highly conducting interwoven SWCNT network not only facilitates electron conduction but also buffers the strain applied to Fe2O3 nanoparticles during the lithiation and delithiation. These results demonstrate the great potential of this hybrid membrane anode for high-performance flexible lithium ion batteries.

Facile Synthesis of Platinum Nanoflower Monolayer on Single-Walled Carbon Nanotube Membrane

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