Carbon Nanotube Forests Research Articles

Electrochemical detection of lead ions using carbon nanotube post electrodes

Heavy metal ions above their recommended limits are highly toxic to human health. Even at low levels, contaminants such as Pb in drinking water can severely affect vulnerable population of the society. Therefore, developing rapid, effective, stable, and convenient sensors for Pb detection has gained significant attention. In this study, considering the excellent properties of carbon nanotubes (CNTs), CNT post electrodes were fabricated by embedding them in a nonconducting polymer. The CNT posts were derived from a closely packed CNT forest with a diameter of 0.3 mm containing millions of vertically aligned pillars. The highly stable CNT post electrodes were employed for the electrochemical sensing of heavy metal ions in 0.1 M citric acid. A linear range of 9.64–168.7 nM (2–35 ppb) was observed for Pb ions. Further, linear ranges of 0.0786–7.86 μM (5–500 ppb) and 15.73–157.36 μM (1000–10000 ppb) were also obtained for Cu ions. Notably, the electrode containing a single CNT post was capable of the electrochemical detection of Pb ions at the ppb level. With this electrode, the sensitivity and limit of detection were 0.5095nA/nM and 2 nM (0.5 ppb) for Pb ions, and 24.53 μA/ppb and 41.67 nM (2.64 ppb) for Cu ions, respectively. The limit of detection for Pb ions is lower than the maximum permissible limit in drinking water set by the World Health Organization. Due the electrochemical method employed on its detection, the reported sensor can simultaneously detect Pb, Cu and Zn ions in tap water.

Water assisted atmospheric CVD super growth of vertically aligned CNT forest for supercapacitor application

We report a high growth rate (37 μm/min) synthesis of vertically aligned carbon nanotube (VACNT) forest, achieving remarkable height exceeding a millimetre with good crystallinity. VACNTs with few numbers of walls have been grown over Fe–Co/Al2O3/SiO2 coated Si wafer using the water assisted atmospheric pressure chemical vapour deposition (WACVD) method. The key to this success lies in the synergistic combination of a bimetallic catalyst (Fe-Co) with buffer Al2O3 layer and the WACVD method. Notably, the VACNT forest, synthesised at optimized conditions can be directly used without the need for additional post-growth purification processes, eliminating the risk of potential damage to the CNTs. Finally, the VACNT forest exhibits excellent areal capacitance of 133.33 mF/cm2 at a current density of 1 mA/cm2 with outstanding cyclic stability of 130 % @ 3000 cycles.

(Invited) Advancing Carbon Nanotube Synthesis: A Data-Driven Strategy to Overcome Trade-Offs

Materials and their synthesis play pivotal roles in energy storage and conversion. In particular, carbon nanotubes (CNTs) have exhibited potential due to their unique multifunctionality, positioning them as promising elements in this field. However, despite advance in the application of CNTs, challenges persist in both synthesis and processing. The advent of artificial intelligence (AI) has emerged as a transformative tool, empowering researchers and showing promise to expedite scientific breakthroughs. In this presentation, I will briefly discuss our development of a two-stage CNT synthesis process. In addition, I will discuss the application of AI to augment researchers’ capabilities in synthesis and processing. As examples, I will discuss our effort to apply a data-driven approach to attempt to break through synthetic trade-offs in single wall CNT forest growth. I will also discuss our development of a tool to determine dispersants for CNT processing.

CNT forest self-assembly insights from in-situ ESEM synthesis

Understanding and controlling the dynamic self-assembly mechanisms of carbon nanotube (CNT) forests is necessary to advance their technological im-pact. Here, in-situ environmental scanning electron microscope (ESEM) chemical vapor deposition (CVD) synthesis observes in real time the real-time nucleation, assembly, delamination, and self-termination of dense (> 109 CNT/cm2), tall (> 100 μm) CNT forests. Forest synthesis is continuously ob-served from nucleation to self-termination. Assembly forces generated near the substrate detach CNTs from the substrate, which simulation suggests requires between 3 and 12 nN of tensile force. Delamination initiates at both the CNT-catalyst and the catalyst-substrate interfaces, indicating multiple delamination mechanisms. Digital image correlation applied to SEM image sequences measures time-invariant strain within growing forests, indicating that forests grow as rigid bodies after liftoff. The Meta CoTracker algorithm measured CNT growth rates reduce from 50 nm/s to full termination over 150 s. The kinematic behaviors we observe are foundational to understanding the process-structure-property relationships of CNT forests.

Controllable Preparation and Mechanism Study of Easy‐Peel High‐Density and Vertically Aligned Carbon Nanotube Forests

The stripping of carbon nanotube forests (CNTF) is an urgent problem in terms of its application in thermal management and semiconductor devices. The easy‐peel and vertically aligned CNTF is prepared in a two‐step process of high vacuum magnetron sputtering and chemical vapor deposition. Based on the thick alumina buffer layer, CNTF with heights of 100 μm, 300 μm, and 500 μm was prepared by adjusting the magnetron sputtering power. Through SEM observation and calculation, the corresponding densities were 2.5 × 109 cm−2, 6.4 × 109 cm−2, and 1.21 × 1010 cm−2, with an average curvature of 1.64 × 102 m−1, 1.35 × 102 m−1 and 0.53 × 102 m‐−1, respectively. The TEM, XPS, Raman, and TGA were used to investigate the growth mechanism of CNTF. The experimental results show that the catalyst particles annealed under high sputtering power refined with high density can grow a low‐defect, well‐oriented, and high‐density CNTF, and confirm the tip growth route. Further analysis shows that the easy‐peel properties of CNTF depend on the thickness of the alumina layer, the tip growth route, and the tight entanglement between the nanotubes. This paper provides technical guidance and support for the preparation, stripping, and application of monolithic CNTF.

Effects of electrode shape in micro-electro-discharge patterning of carbon nanotube forests

This paper reports the performance of different tool electrode structures in micropatterning of vertically aligned carbon nanotube (CNT) forests through dry micro-electro-discharge machining (μEDM). Micro cylindrical electrodes of tungsten with flat and hemispherically rounded tips were employed in this study. The rounded-tip electrode was shaped using a custom wet μEDM process. Both types of electrodes were used to pattern arrays of micro test slots at different depths and discharge voltages on a multi-walled CNT forest from which the resultant discharge gaps were experimentally characterized. The rounded-tip electrode showed a 2.1–2.4× reduction in the discharge gap with applied voltages of 15–20 V, suggesting its potential to improve the lateral resolution of the patterning process when compared with the flat-tip case. Finite element analysis of the process configuration with these two electrodes was conducted and showed good agreement with the improvement factors of the discharge gap experimentally observed. However, the process using the rounded-tip electrode resulted in larger variations on the bottom surfaces of the created patterns, while the use of the flat-tip electrode provided higher uniformity on these surfaces, revealing an apparent trade-off relationship between the discharge gap and the patterning uniformity for the two electrode types under the tested conditions. Elemental analysis of the processed CNT forest surfaces showed no detectable contamination from the electrodes onto the forest structures patterned using either electrode.

High Selenium Loading in Vertically Aligned Porous Carbon Framework with Visualized Fast Kinetics for Enhanced Lithium/Sodium Storage

AbstractLithium/sodium–selenium (Li/Na–Se) batteries with high volumetric specific capacity are considered promising as next‐generation battery technologies. However, their practical application is hindered by challenges such as low Se loading in cathodes and the polyselenides shuttle effect. To address these challenges, a new Se host is introduced in the form of a free‐standing N, O co‐doped vertically aligned porous carbon framework decorated with a carbon nanotube forest (VCF‐CNTs), allowing for high mass loading of up to 16 mg cm−2. The low‐tortuosity Se@VCF‐CNTs architecture facilitates rapid lithiation/sodiation kinetics, while the CNT forests in vertical microchannels enhance efficient Se loading and serve as a multi‐layer fence to prevent undesired polyselenide shuttling. Consequently, the Se@VCF‐CNTs cathode displays a significant areal capacity of 10.3 mAh cm−2 at 0.1 C with a Se loading of 16 mg cm−2 for Li–Se batteries, exceeding that of commercial lithium ion batteries (4.0 mAh cm−2). In Na–Se batteries, the Se@VCF‐CNTs electrode with a Se loading of 5 mg cm−2 exhibits a discharge capacity of 436 mAh g−1 after 200 cycles, proving its consistent cycling performance. This study enriches the field of knowledge concerning high‐loading Se‐based battery systems, offering a promising avenue for enhancing energy density in the field.

Continuous Reactive-Roll-to-Roll Growth of Carbon Nanotubes for Fog Water Harvesting Applications

A simple method is presented for the continuous generation of carbon nanotube forests stably anchored on stainless-steel surfaces using a reactive-roll-to-roll (RR2R) configuration. No addition of catalyst nanoparticles is required for the CNT-forest generation; the stainless-steel substrate itself is tuned to generate the catalytic growth sites. The process enables very large surfaces covered with CNT forests to have individual CNT roots anchored to the metallic ground through primary bonds. Fog water harvesting is demonstrated and tested as one potential application using long CNT-covered wires. The RR2R is performed in the gas phase; no solution processing of CNT suspensions is used, contrary to usual R2R CNT-based technologies. Full or partial CNT-forest coverage provides tuning of the ratio and shape of hydrophobic and hydrophilic zones on the surface. This enables the optimization of fog water harvesters for droplet capture through the hydrophobic CNT forest and water removal from the hydrophilic SS surface. Water recovery tests using small harp-type harvesters with CNT-forest generate water capture of up to 2.2 g/cm2·h under ultrasound-generated fog flow. The strong CNT root anchoring on the stainless-steel surfaces provides opportunities for (i) robustness and easy transport of the composite structure and (ii) chemical functionalization and/or nanoparticle decoration of the structures, and it opens the road for a series of applications on large-scale surfaces, including fog harvesting.

Impact of dynamic density decay of growing carbon nanotube forests on electrical resistivity

Vertically aligned carbon nanotube (CNT) forests densely formed on diverse metallic substrates are desirable as large-area electrodes and thermal interface materials. In this study, we achieved high-density CNT forests on stainless steel and Cu substrates by preventing the interaction between the metallic elements and Fe catalysts at high temperatures. We found that coating the substrate surface with a combination of Ta and SiO2 effectively suppressed the diffusion of metallic elements of the substrate to the catalytic layer. The macroscopic electrical resistivity of longer forests was found to increase as the number density of CNTs decreased during the growth process. This increase in resistivity was reproduced by the dynamic density decay model in which CNT density decreases with forest growth. We point out the importance of the relationship between the length and density of CNT forests for applications.

Significantly enhanced laser trapping and heating of carbon nanotube/carbon fibre hierarchical composites for efficient laser-assisted automated fibre placement

Laser-assisted automated fibre placement (LAFP) process is promising for manufacturing large-scale thermoplastic composite parts. However, its laydown speed suffers from the near-infrared (NIR) laser reflection from carbon fibres (CFs) and the high specific heat capacity of prepregs. Herein, the light-trapping carbon nanotube (CNT) forest was grown on CFs using a low-cost flame synthesis process, followed by its embedding in the poly-ether-ether-ketone (PEEK) matrix to produce CF/PEEK/CNTs prepregs with simultaneously enhanced laser absorption and reduced specific heat capacity. Spectroscopic analysis shows that CNTs reduce the NIR reflectance of prepregs due to enhanced light-trapping efficiency with hierarchical CNT/CF structures, further evidenced by a transition from diffuse reflection to specular reflection. Additionally, CNTs reduce 19 % of the specific heat capacity by restricting polymer chain movement. Therefore, the hierarchical structure increases the heating rate and maximum temperature of CF/PEEK prepregs by 18.5 % and 16.0 %, respectively, under 1080 nm laser radiation during the LAFP process.

Addressing the Trade-Off between Crystallinity and Yield in Single-Walled Carbon Nanotube Forest Synthesis Using Machine Learning.

Synthetic trade-offs exist in the synthesis of single-walled carbon nanotube (SWCNT) forests, as growing certain desired properties can often come at the expense of other desirable characteristics such as the case of crystallinity and growth efficiency. Simultaneously achieving mutually exclusive properties in the growth of SWCNT forests is a significant accomplishment, as it requires overcoming these trade-offs and balancing competing mechanisms. To address this, we trained a machine-learning regression model with a set of 585 "real" experimental synthesis data, which were taken using an automatic synthesis reactor. Subsequently, 16000 exploratory "virtual" experiments were performed by our trained model to examine potential routes toward addressing the current crystallinity-height trade-off limitation, and suggestions on growth conditions were predicted. Importantly, additional validation using "real" experimental syntheses showed good agreement with the predictions as well as a 48% increase in growth efficiency while maintaining the high crystallinity (G/D-ratio). This highlighted the effectiveness and accuracy of the predictive capability of our machine-learning model, which achieved improved results in less than 50 validation tests. Furthermore, the trained model revealed the surprising importance of the nature of the carbon feedstock, particularly the reactivity and concentration, as a route for overcoming the trade-off between the SWCNT crystallinity and growth efficiency. These results of the high-efficiency synthesis of highly crystalline SWCNT forests represent a significant advance in overcoming synthetic trade-off barriers for complex multivariable systems.

Conductive 3D nano-biohybrid systems based on densified carbon nanotube forests and living cells

Conductive biohybrid cell-material systems have applications in bioelectronics and biorobotics. To date, conductive scaffolds are limited to those with low electrical conductivity or 2D sheets. Here, 3D biohybrid conductive systems are developed using fibroblasts or cardiomyocytes integrated with carbon nanotube (CNT) forests that are densified due to interactions with a gelatin coating. CNT forest scaffolds with a height range of 120–240 µm and an average electrical conductivity of 0.6 S/cm are developed and shown to be cytocompatible as evidenced from greater than 89% viability measured by live-dead assay on both cells on day 1. The cells spread on top and along the height of the CNT forest scaffolds. Finally, the scaffolds have no adverse effects on the expression of genes related to cardiomyocyte maturation and functionality, or fibroblast migration, adhesion, and spreading. The results show that the scaffold could be used in applications ranging from organ-on-a-chip systems to muscle actuators.Graphical abstract

Kinetics of Light-Responsive CNT / PNIPAM Hydrogel Microactuators.

Light-responsive microactuators composed of vertically aligned carbon nanotube (CNT) forests mixed with poly(N-isopropylacrylamide) (PNIPAM) hydrogel composites are studied. The benefit of this composite is that CNTs act as a black absorber to efficiently capture radiative heating and trigger PNIPAM contraction. In addition, CNT forests can be patterned accurately using lithography to span structures ranging from a few micrometers to several millimeters in size, and these CNT-PNIPAM composites can achieve response times as fast as 15ms. The kinetics of these microactuators are investigated through detailed analysis of high-speed videos. These are compared to a theoretical model for the deswelling dynamics, which combines thermal convection and polymer diffusion, and shows that polymer diffusion is the rate-limiting factor in this system. Applications of such CNT/hydrogel actuators as microswimmers are discussed, with light-actuating micro-jellyfish designs exemplified, and >1500 cycles demonstrated.

Ultrathin, Large‐Area, and Multifunctional Polarizer Based on Highly Ordered Carbon Nanotubes Produced by Simple Shear Flow

AbstractAligning carbon nanotubes (CNTs) with high orientational ordering in a 2D array is essential for realizing optical polarizers with high polarization efficiency over a wide spectral range. Two methods are reported: dispersing CNTs in a polymer matrix followed by stretching, and mechanical stretching of a vertically grown CNT forest and then transferring it onto a substrate. However, neither can realize nanometer‐thin or large polarizers. Herein, a novel approach is demonstrated to construct a large and thin (150 nm) conductive CNT polarizer by achieving liquid crystal (LC) phase of size‐controlled CNTs in chlorosulfonic acid, unidirectional shearing, and then drying. The polarizer exhibits an excellent polarization efficiency of 98.4% for ultraviolet (365 nm) and 96.0% for visible light (550 nm). This performance is maintained even at 400 °C, while the conventional iodine‐type polarizer starts to lose efficiency over 100 °C. The CNT polarizer with high polarization efficiency for UV can replace the costly nano‐patterned wire‐grid polarizers currently used for photoaligning LCs and also its multifunction playing role of polarizer, electrode, and LC alignment is confirmed with switching of LC device. This study provides a new paradigm for realizing ultrathin and large CNT polarizers for broadband applications with outstanding heat resistance.

Thick Architected Silicon Composite Battery Electrodes Using Honeycomb Patterned Carbon Nanotube Forests

To meet the growing performance demands for personal electronics and electric vehicles the energy density of lithium-ion batteries can be increased by incorporating thicker electrodes. We present thick “honeycomb” electrodes based on patterned, vertically aligned carbon nanotubes (CNTs) on Cu foils. Thick electrodes are created by Si deposition on >100 μm tall honeycomb patterned CNTs. Si-CNT electrodes are cycled in half-cells, demonstrating electronic connection between the Si and Cu foil via the aligned CNTs. For ~4.7 mAh cm−2 capacity the honeycomb patterning improves capacity retention (78%) over 30 cycles compared to non-patterned electrodes (58%). We attribute this improvement to the honeycomb’s ability to accommodate Si expansion, thereby reducing cracking that causes active material loss and solid electrolyte interphase instability, and to provide pathways for Li-ion transport into the electrode. The Si-CNT electrode capacity is further increased to 20 mAh cm−2 by increasing the Si loading. Finally, a fluoroethylene carbonate containing electrolyte is used to increase cell lifetime. Here, the honeycomb electrodes have a higher areal (~10.2 mAh cm−2) and retained (65%) capacity over 180 cycles, and exhibit superior rate performance to their non-patterned counterparts. Our work demonstrates the role of patterning in enabling aligned CNTs as a robust template for thick battery electrodes.

Free-Standing CNT Film for Interlaminar Toughening: Insight into Infiltration and Thickness Effects.

Carbon fiber reinforced polymer composites have the advantages of being lightweight, having high strength and designability, and having been extensively used. However, the interlaminar toughness and delamination resistance of these composites are relatively poor due to their laminated structure and intrinsic brittleness of resin matrix. In this paper, commercialized free-standing carbon nanotube (CNT) films, drawn from CNT forests, were used to toughen the interlaminar interfaces of the composites. The effects of resin infiltration state and thickness of CNT films on the interlaminar toughening effect were systematically investigated. The results show that the pre-infiltration treatment of CNT films with acetone diluted epoxy resin solution can effectively improve the degree of resin infiltration. Compared with the samples containing untreated CNT film, the Mode I and Mode II interlaminar fracture toughness of the treated samples were significantly improved. The GIC reached a maximum of 1412.42 J/m2 at a CNT film thickness of 5 µm, which was about 61.38% higher than that of the baseline. At a CNT film thickness of 15 µm, the GIIC reached a maximum value of 983.73 J/m2, approximately 67.58% higher than that of the baseline. The corresponding toughening mechanisms were also systematically analyzed.

Optimizing platinum-free counter electrodes for dye-sensitized solar cells: Multiwalled carbon nanotube forests covered with ruthenium layers

Multiwalled carbon nanotube (MWCNT) forests have extremely large surface areas and high catalytic activity. To use them as alternative materials for Pt/fluorine-doped tin oxide (FTO) conventional counter electrodes (CEs) in dye-sensitized solar cells (DSSCs), a unique Ru metal layer, prepared with 600-cycle atomic layer deposition, was employed. The best Ru-coated MWCNT forest (Ru/MWCNT) CE performance was achieved by examining the experimental conditions for the MWCNT forests, including deposition processes, catalyst thicknesses and synthesis time. The results revealed that 20μm-thick MWCNT forests with numerous defects/disordered sites exhibit excellent CE performance. In practice, Ru/MWCNT CEs prepared under optimal synthesis conditions show low charge transfer resistance (Rct of approximately 2.5 ohm) and series resistance (Rs of approximately 14 ohm) that are even better than those for Pt/FTO CEs (Rct=6.36 ohm and Rs=16.4 ohm). Owing to these excellent Rct and Rs values, dye-sensitized solar cells with optimized Ru/MWCNT CEs showed better performance than those containing Pt/FTO CEs. Finally, post-heat treatment of Ru/MWCNT CEs increased the cell efficiency of the DSSCs.

Customizing 3D Structures of Vertically Aligned Carbon Nanotubes to Direct Neural Stem Cell Differentiation.

Neural tissue-related illnesses have a high incidence and prevalence in society. Despite intensive research efforts to enhance the regeneration of neural cells into functional tissue, effective treatments are still unavailable. Here, a novel therapeutic approach based on vertically aligned carbon nanotube forests (VA-CNT forests) and periodic VA-CNT micropillars produced by thermal chemical vapor deposition is explored. In addition, honeycomb-like and flower-like morphologies are created. Initial viability testing reveals that NE-4C neural stem cells seeded on all morphologies survive and proliferate. In addition, free-standing VA-CNT forests and capillary-driven VA-CNT forests are created, with the latter demonstrating enhanced capacity to stimulate neuritogenesis and network formation under minimal differentiation medium conditions. This is attributed to the interaction between surface roughness and 3D-like morphology that mimics the native extracellular matrix, thus enhancing cellular attachment and communication. These findings provide a new avenue for the construction of electroresponsive scaffolds based on CNTs for neural tissue engineering.

Investigating the Electromechanical Sensitivity of Carbon-Nanotube-Coated Microfibers.

The piezoresistance of carbon nanotube (CNT)-coated microfibers is examined using diametric compression. Diverse CNT forest morphologies were studied by changing the CNT length, diameter, and areal density via synthesis time and fiber surface treatment prior to CNT synthesis. Large-diameter (30-60 nm) and relatively low-density CNTs were synthesized on as-received glass fibers. Small-diameter (5-30 nm) and-high density CNTs were synthesized on glass fibers coated with 10 nm of alumina. The CNT length was controlled by adjusting synthesis time. Electromechanical compression was performed by measuring the electrical resistance in the axial direction during diametric compression. Gauge factors exceeding three were measured for small-diameter (<25 μm) coated fibers, corresponding to as much as 35% resistance change per micrometer of compression. The gauge factor for high-density, small-diameter CNT forests was generally greater than those for low-density, large-diameter forests. A finite element simulation shows that the piezoresistive response originates from both the contact resistance and intrinsic resistance of the forest itself. The change in contact and intrinsic resistance are balanced for relatively short CNT forests, while the response is dominated by CNT electrode contact resistance for taller CNT forests. These results are expected to guide the design of piezoresistive flow and tactile sensors.

A Stretchable Glucose Sensor via Conductive Polymer-Coated VACNT Forests Rooted in Elastomer Polymer Substrate

This paper presents a stretchable glucose sensor composed of dodecylbenzenesulfonate-doped polypyrrole (PPyDBS)-coated vertically aligned carbon nanotube (VACNT) forests rooted in polydimethylsiloxane (PDMS) substrate. The measured sensitivity was approximately 10 mA cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-2</sup> M <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-1</sup> with a wide linear range demonstrated, as low as 0.1 mM and up to 12 mM, and the sensor achieved 90% of steady-state current in less than 3 seconds. The PDMS/CNT/PPy(DBS)/GOx structure was tested under stretching, demonstrating the coefficients of determination larger than 0.982, indicating its robustness of sensing capability of glucose concentrations with tensile strain up to 75%. These results show the potential of this stretchable glucose sensor with a novel fabrication strategy and stretchable electrode design toward potential wearable applications interfacing with physiological fluids.