Free-standing Multi-walled Carbon Nanotubes Research Articles

Densification Induced Decoupling of Electrical and Thermal Properties in Free-Standing MWCNT Films for Ultrahigh p- and n-Type Power Factors and Enhanced ZT.

Generating sufficient power from waste heat is one of the most important things for thermoelectric (TE) techniques in numerous practical applications. The output power density of an organic thermoelectric generator (OTEG) is proportional to the power factors (PFs) and the electrical conductivities of organic materials. However, it is still challenging to have high PFs over 1mWm-1 K-2 in free-standing films together with high electrical conductivities over 1000Scm-1 . Herein, densifying multi-walled carbon nanotube (MWCNT) films would increase their electrical conductivity dramatically up to over 10000Scm-1 with maintained high Seebeck coefficients >60µVK-1 , thus leading to ultrahigh PFs of 7.25 and 4.34mWm-1 K-2 for p- and n-type MWCNT films, respectively. In addition, it is interesting to notice that the electrical properties increase faster than the thermal conductivities, resulting in enhanced ZT of 3.6 times in MWCNT films. An OTEG made of compressed MWCNT films is fabricated to demonstrate the heat-to-electricity conversion ability, which exhibits a high areal output power of ∼12 times higher than that made of pristine MWCNT films. This work demonstrates an effective way to high-performance nanowire/nanoparticle-based TE materials such as printable TE materials comprised of nanowires/nanoparticles.

Plasma-enhanced atomic layer deposition of ruthenium metal on free-standing carbon nanotube forest for 3D flexible binder-less supercapacitor electrodes

Plasma-enhanced atomic layer deposition of ruthenium on functionalized free-standing multi-walled carbon nanotube (MWCNT) forest directly grown on a stainless steel mesh as a flexible supercapacitor electrode is done by a zero-oxidation state precursor and nitrogen plasma. Using this method for the fabrication of 3D flexible supercapacitor electrodes eliminates the need for any binder component and solution-based synthesis step as well as the production of any toxic by-products. Moreover, it enables the utilization of the entire high-surface-area MWCNTs and it alleviates the Ru agglomeration issue typically found in solution-based synthesis techniques. Accordingly, ruthenium is successfully deposited on the entire length of the carbon nanotubes in various process temperatures and plasma exposure durations with a thickness range of 15–60 nm. Electrochemical characterization of the electrodes shows a significant improvement in the capacitance of Ru coated MWCNT compared to bare MWCNT due to the additional surface faradaic redox reactions. Cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS) are carried out to evaluate the electrochemical performance of the fabricated electrodes. The capability of the 3D flexible electrode is evaluated in different bending angles of 60, 80, and 180° and twisting conditions. Capacitance as high as 1834.5 mF.cm−2 (393 F.g−1) with a very low charge transfer resistance of 5.49 Ω.cm−2 is achieved that shows >400 % improvement in capacitance compared to bare MWCNTs. A capacitance retention of 92 % after 1000 CV cycles is achieved.

Fabrication of a Free-Standing MWCNT Electrode by Electric Field Force for an Ultra-Sensitive MicroRNA-21 Nano-Genosensor.

Abnormal expression of microRNA-21 (miR-21) is considered to be closely associated with the pathogenesis of colorectal cancer. However, great challenges do exist for the development of ultra-sensitive biosensors to detect the abnormal expression of miR-21 due to the low concentration in serum (fm level) at the early stage of colorectal cancer. Therefore, electric field force is used to rotate and rearrange random multi-walled carbon nanotubes (MWCNTs) at the microscale to improve the active sites of the electrode in this study. The free-standing MWCNTs are densely and high-orderly embedded into the bare electrode along the direction of the electric field. Compared to the bare electrode, the peak-current response of the free-standing MWCNT electrode improves by 150times in cyclic voltammetric measurement. A nano-genosensor based on the free-standing MWCNT electrode is developed for measuring miR-21. The nano-genosensor for miR-21 shows an ultra-high sensitivity of 48.24 µA µm-1 , a wide linear range from 0.01 × 10-15 to 100 × 10-12 m, and a low detection limit of 1.2 × 10-18 m. The present nano-genosensor shows superior performance for miR-21 in human serum samples and demonstrates a potential application for the diagnosis of early stage colorectal cancer.

Anomalous nonlinear terahertz transmission of photoexcited carbon nanotubes

We demonstrate that free-standing multi-walled carbon nanotubes exhibit extraordinary nonlinear terahertz responses upon optical excitation. Terahertz transmission of the photoexcited nanotubes rises in a narrow range of intermediate intensity with increasing intensity, while falling in the regime of low and high intensities. A theoretical analysis shows that the nanotube conductivity drops sharply in the region of intermediate intensity and soars elsewhere. Field-effect mobility and field-induced carrier multiplications are considered to be competing processes governing the rise and fall of the conductivity.

Smooth surface induced glossy appearance of freestanding multiwall carbon nanotube sheet

Carbon nanotube (CNT) structures reported in the literature often have a black color with low reflectance and matt surface appearance. Only a few papers reported the high reflectance and glossy appearance of the CNT surface on a substrate. To our knowledge, no one has reported the glossy appearance of freestanding CNT. Herein, we have successfully fabricated a freestanding multi-walled CNT sheet with a glossy or mirror-like surface appearance. Raman spectroscopy confirmed that both matt and glossy freestanding CNT sheets have the same chemical composition. We found that the glossy freestanding CNT sheet has a relatively flat surface morphology compared to matt freestanding CNT sheet, as seen in the atomic force microscopy results. We attributed the glossy appearance due to a relatively flat surface morphology of the freestanding CNT sheet.

Slippage-inhibiting effect of interfacial cross-linking of nanotubes by defluorination on the mechanical properties of free-standing multi-walled carbon nanotube yarns: Comparison with individual multi-walled carbon nanotubes

Carbon nanotube yarns (CNTYs) spun only by twisting have a low mechanical strength due to the slippage of individual CNTs. This hinders the practical applications of CNTYs. Here, we studied the slippage-inhibiting effect of the interfacial cross-linking of the nanotubes by defluorination on the mechanical properties of free-standing MWCNTYs and compared with the fracture tensile strength of the individual defluorinated MWCNTs. The mechanical properties of defluorinated MWCNTYs increased with increasing annealing temperature, and MWCNTYs defluorinated at 800 °C under a pressure of 76 Pa (p-deF800-MWCNTYs) exhibited an average specific fracture strength of 0.69 N/tex and an average specific fracture stiffness of 103.2 N/tex, with high flexibility. As the fracture tensile strength of individual defluorinated MWCNTs was low, the high strength of the p-deF800-MWCNTYs was attributed to the cross-linking of the active carbon atoms in the outer nanotubes with those of the adjacent nanotubes through sp2C and sp3C bonds, which led to the transfer of load to the yarns. Thus, the results of our study highlight the importance of good balance between the defects of CNTs and cross-linking between CNTs.

Preparation of diameter-controlled free-standing MWCNT membranes and their application for dye adsorption.

The synthesis of multi-walled carbon nanotubes (MWCNTs) was carried out over different Ni-loaded metallic oxide catalyst nanoparticles and under different reduction times to control the outside diameter of the nanotubes. Moreover, high-purity, free-standing membranes were fabricated by a simple filtration of the as-grown MWCNTs. Furthermore, the dye-adsorption properties of the nanotubes depended on the diameter of the carbon nanotubes (CNTs). The adsorption isotherms and kinetics of anionic dyes could be described by Freundlich and pseudo-second-order models, respectively. Thermodynamic studies suggested that the adsorption processes were spontaneous and exothermic. This work provides new insights into the synthesis and application of MWCNTs with the selective adsorption properties of carbon-based materials for the removal of organic dyes.

Free-standing flexible multiwalled carbon nanotubes paper for wearable thermoelectric power generator

Most of the thermoelectric research, these days, is being focussed towards development of flexible thermoelectric power generators (TEG) for wearable applications. Organic thermoelectric materials being flexible and solution processable, though, seem promising cannot render themselves for designing of conventional thermoelectric devices which require both p- and n-type of legs; due to lack of air-stable and flexible n-type materials. This work shows the possibility of conversion of a p-type flexible free-standing multiwalled carbon nanotubes (MWCNTs) paper into n-type on treatment with polyethylenimine (PEI). X-ray photoelectron spectroscopy results suggest that ‘as-grown’ MWCNTs attained n-type nature due to electron donation by imine group of PEI. Power factors of ~0.2 and ~0.06 μW/mK2 observed respectively for p- and n-type MWCNTs papers, owing to extremely low thermal conductivity (~0.05W/mK), resulted in figure-of-merit (ZT) of 1.27 × 10−3 and 3.02 × 10−4 at 68 °C. A prototype TEG designed using ‘as-grown’ and ‘PEI-modified’ MWCNTs as p- and n-type thermoelements respectively exhibited output of 227 μV/7.6 μA for a temperature difference of 40 °C. In short, facile scalability of MWCNTs when collaborated with such a low cost, environment friendly method that can easily modify its conduction to n-type can certainly open opportunities for scalable production of flexible roll-to-roll type wearable thermoelectric modules.

Heat Exchange Structures Based on Copper/CNT Composite

In this study different types of multi-walled carbon nanotubes (MWCNT) were produced by the fixed bed and aerosol chemical vapor deposition (CVD) method. Nanocomposite materials were prepared by incorporation of different MWCNTs in copper matrix using powder metallurgy methods. By using hot pressing in combination with hot extrusion, the orientation of the carbon reinforcement was tuned from 3D to 1D alignment. After a selective etching process the carbon reinforcement is partially free-standing at the composite surface, but still embedded in the metal matrix. The engineered surface acts almost like a black body. The spectral evaluation of the surface functionalization will be shown for wavelengths from 200 nm to 20 µm. These results are compared to bulk copper. The free-standing MWCNT also behave like fins/pins in heat exchanger structures or surface enhancement in pool boiling. The experimental setup will be explained and the measurement described for pure copper. The theoretical heat transfer coefficient of the engineered surface is calculated depending on diameter and length of the free-standing MWCNTs. The results are compared to bulk copper.

Tailoring terahertz surface plasmon wave through free-standing multi-walled carbon nanotubes metasurface

Surface plasmons have a fundamental role in the dynamics of photon-electron interactions and in optical metamaterials. Terahertz (THz) time-domain spectroscopy was used to characterize the complex dielectric constant, index of refraction, and conductivity of super-aligned, free-standing, multi-walled carbon nanotube films over the range 0.2-2.5 THz. These complex parameters were in excellent agreement with Maxwell-Garnett and Drude-Lorentz models. In addition, surface plasmon excitations in engineered, subwavelength, multi-walled carbon nanotube metasurfaces were examined. The observed surface plasmon resonances, reproduced by simulation, could be changed over the THz frequency range by altering the lattice constant of the arrays. The THz transmission was enhanced at the resonance peak. Overall, the results indicate potential applications for THz metasurfaces based on super-aligned, free-standing multi-walled carbon nanotubes.

Free-Standing Binder-Free Multi-Wall Carbon Nanotube/Silicon Anodes for Lithium-Ion Batteries

Silicon is of interest owing to its high theoretical capacity (4200 mAh/g). However, its enormous volume expansion of silicon during cycling is one of the main reasons for the rapid capacity fading and pulverisation of the anode commonly observed. Here, freestanding multi-wall carbon nanotube (MWCNT)/silicon anodes were prepared using so-called MWCNT buckypapers (BPs) as current collectors instead of the traditional metallic foils. To prepare the anodes, silicon was deposited on these MWCNT BPs to form silicon nanoparticles (SiNPs) and subsequent annealing resulted in the formation of a connecting SiC interface preventing the SiNPs from detaching. An amorphous carbon coating was applied in order to enhance electrical conductivity and overall integrity of these hierarchical anode materials. The morphology and chemical composition of the Si-BP anodes were characterised by means of SEM, TEM, EDX, STEM, XRD, RAMAN, etc. Cycling tests of these binder and additive-free anodes revealed an areal capacity of 0.55 mAh/cm2 after 300 cycles with 99.7% of Columbic efficiency and showed that the presence of the SiC interface and a-C coating played a crucial role in improving their rate capability and stability.

Development of Surface‐Engineered Tape‐Casting Method for Fabricating Freestanding Carbon Nanotube Sheets Containing Fe2O3 Nanoparticles for Flexible Batteries

Chemical vapor deposition and filtration are commonly used to fabricate freestanding multiwalled carbon nanotube sheets containing iron(III) oxide (Fe2O3) (MWCNT–Fe2O3 sheets). However, the former is relatively expensive, and the latter suffers from poor scalability. Here, the authors develop an inexpensive, scalable, high‐throughput, tunable tape‐casting method for fabricating flexible, foldable freestanding MWCNT–Fe2O3 sheets. When tested as electrodes in lithium‐ion batteries, the sheets perform better than conventional graphite on copper foil (681 mAh g−1 after 20 cycles at 100.5 mA g−1/0.1 C‐rate vs. 72.5 mAh g−1 after 20 cycles at 37.2 mA g−1/0.1 C‐rate). Sheets prepared at Fe2O3:MWCNT mass ratios ranging from 1/4 to 2/1 are flexible and easy to be separated from the substrate, but a sheet prepared at a 9/1 ratio is not. The ratio can be tuned to suit various applications. Sheets with high (low) Fe2O3:MWCNT mass ratios has high (low) charge‐transfer resistance and are suitable for applications requiring high energy density (high power density). Mechanical compression of the sheets flattens them and increase their density from 0.449 to 0.771 g cm−3, which in turn increases their electrical conductivity from 3.56 × 103 to 5.73 × 103 S m−1.

Free-standing carbon nanotubes as non-metal electrocatalyst for oxygen evolution reaction in water splitting

Oxygen evolution reaction (OER) has significant impact on the overall electrochemical water splitting. We introduce, for the first time, a facile approach towards the fabrication of versatile electrode composed of free-standing multiwalled carbon nanotubes (MWCNTs) as electrocatalyst for the water splitting reaction. Directly extracted MWCNTs as sheets from vertically grown arrays transferred over the glass substrate, are used without any post treatment as a working electrode for OER. Onset potential of 1.60 V was achieved for MWCNTs which is significantly reduced as compared to platinum based metal electrode (1.72 V) with excellent current density. No surface modification, metal-free nature, flexibility and low cost with excellent catalytic activity proved this material as a promising candidate for the replacement of metal based electrodes in electrochemical water splitting.

Free-standing flexible MWCNTs bucky paper: Extremely stable and energy efficient supercapacitive electrode

Due to highly conducting and extraordinary stable nature, carbon based materials expand the arms of energy storage devices in terms of supercapacitor. Hence, emphasis has been made to use flexible and free-standing multi-walled carbon nanotubes (MWCNTs) bucky paper synthesized by chemical vapor deposition for electrochemical supercapacitive electrode. The high specific capacitance of 270F/g (2mV/s) with superb stable behavior (88% at 10000 cycles) of bucky paper has promised as decent electrode in energy storage application. Aqueous symmetric supercapacitor (ASSC) device developed through bucky paper exhibits voltage frame of 1.6V yielding specific capacitance of 91F/g along with specific energy of 32 Wh/kg at a current density of 1mA/cm2 with trustworthy stability of 107% at 6000 cycles. The hands-on practicability to light up a red LED offers its promising approach in energy storage domain.

Structural and mechanical properties of free-standing multiwalled carbon nanotube paper prepared by an aqueous mediated process

Free-standing carbon nanotube film (bucky paper) is a very important material for various applications, but its commercial production is still limited due to size, cost and properties. In the present work, different methods are used to prepare five different types of bucky papers, namely normal, pure refluxed, oxidized, oxidized refluxed and functionalized by using as-produced multiwalled carbon nanotubes (MWCNTs), refluxed MWCNTs, air-oxidized MWCNTs, oxidized refluxed MWCNTs and HNO3 functionalized MWCNTs, respectively. Morphological, physical and structural changes appeared due to different methods are analysed by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction spectroscopy and Raman spectroscopy. Changes in the relative characteristic peak ratio (i.e. IG/ID, IG′/ID and IG′/IG) as a function of MWCNTs quality are determined. It is observed that oxidized refluxed MWCNTs have an average value of IG/ID, IG′/ID and IG′/IG ratio as 4.12, 7.15 and 1.71, respectively, which is higher as compared to other samples. The mechanical properties of different bucky papers are studied by performing tensile tests. The result showed that tensile strength, Young’s modulus and toughness of oxidized refluxed MWCNTs bucky paper are 3.9 MPa, 440 MPa and 780 Jm−3, respectively, which are higher as compared to as-produced MWCNTs bucky paper. The air oxidation and back-to-back refluxing generates nanoscale irregularities within the hexagonal C-structure of a nanotube wall. This helps in improving intermolecular bonding and packing which resulted into significant improvement in the mechanical properties. These bucky papers prepared by economical ways of air oxidation and refluxing in an alkali-soluble emulsifier assisted aqueous medium are potential candidates for field emission devices, energy storage devices and structural materials.

Freestanding Aligned Multi-walled Carbon Nanotubes for Supercapacitor Devices

We report on the synthesis and electrochemical properties of multi-walled carbon nanotubes (MWCNTs) for supercapacitor devices. Freestanding vertically-aligned MWCNTs and MWCNT powder were grown concomitantly in a one-step chemical vapour deposition process. Samples were characterized by scanning and transmission electron microscopies and Fourier transform infrared and Raman spectroscopies. At similar film thicknesses and surface areas, the freestanding MWCNT electrodes showed higher electrochemical capacitance and gravimetric specific energy and power than the randomly-packed nanoparticle-based electrodes. This suggests that more ordered electrode film architectures facilitate faster electron and ion transport during the charge–discharge processes. Energy storage and supply or supercapacitor devices made from these materials could bridge the gap between rechargeable batteries and conventional high-power electrostatic capacitors.

Anisotropic high-field terahertz response of free-standing carbon nanotubes

We demonstrate that unidirectionally aligned, free-standing multi-walled carbon nanotubes (CNTs) exhibit highly anisotropic linear and nonlinear terahertz (THz) responses. For the polarization parallel to the CNT axis, strong THz pulses induce nonlinear absorption in the quasi-one-dimensional conducting media, while no nonlinear effect is observed in the perpendicular polarization configuration. Time-resolved measurements of transmitted THz pulses and a theoretical analysis of the data reveal that intense THz fields enhance permittivity in carbon nanotubes by generating charge carriers.

Anisotropic Properties of Ultra-Thin Freestanding Multi-Walled Carbon Nanotubes Film for Terahertz Polarizer Application

Anisotropic transmission of ultrathin freestanding multi-walled carbon nanotubes (MWCNTs) film has been investigated using terahertz (THz) time-domain spectroscopy. The super-aligned MWCNTs films were fabricated by a novel method—drawing and winding carbon nanotubes on square-shaped polytetrafluoroethylene (PTFE) frame. The MWCNTs film exhibited anisotropic transmittance of THz wave depending on the alignment direction of carbon nanotubes relative to the THz wave polarization orientation, which proved that such MWCNTs film acts as an ideal polarizer in the THz regime. The degree of polarization (DOP) of 99.4% and the extinction ratio (ER) of 25.3 dB (average value) has been demonstrated for a MWCNTs film of 9- <formula formulatype="inline" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex Notation="TeX">$\mu\hbox{m}$</tex></formula> thickness in a wide frequency range from 0.1 to 2.5 THz. Furthermore, the value of DOP and ER can be engineered expediently by controlling the film thickness. Our approach opens the possibility of MWCNTs film in application of THz optoelectronic devices.

Carbon Nanotubes Released from an Epoxy-Based Nanocomposite: Quantification and Particle Toxicity.

Studies combining both the quantification of free nanoparticle release and the toxicological investigations of the released particles from actual nanoproducts in a real-life exposure scenario are urgently needed, yet very rare. Here, a new measurement method was established to quantify the amount of free-standing and protruding multiwalled carbon nanotubes (MWCNTs) in the respirable fraction of particles abraded from a MWCNT-epoxy nanocomposite. The quantification approach involves the prelabeling of MWCNTs with lead ions, nanocomposite production, abrasion and collection of the inhalable particle fraction, and quantification of free-standing and protruding MWCNTs by measuring the concentration of released lead ions. In vitro toxicity studies for genotoxicity, reactive oxygen species formation, and cell viability were performed using A549 human alveolar epithelial cells and THP-1 monocyte-derived macrophages. The quantification experiment revealed that in the respirable fraction of the abraded particles, approximately 4000 ppm of the MWCNTs were released as exposed MWCNTs (which could contact lung cells upon inhalation) and approximately 40 ppm as free-standing MWCNTs in the worst-case scenario. The release of exposed MWCNTs was lower for nanocomposites containing agglomerated MWCNTs. The toxicity tests revealed that the abraded particles did not induce any acute cytotoxic effects.

Electrodeposition of Various Au Nanostructures on Aligned Carbon Nanotubes as Highly Sensitive Nanoelectrode Ensembles

An efficient method has been developed to synthesize well-aligned multi-walled carbon nanotubes (MWCNTs) on a conductive Ta substrate by chemical vapor deposition. Free-standing MWCNTs arrays were functionalized through electrochemical oxidation with the formation of hydroxyl and carboxyl functional groups. Facile template-free electrochemical routes were then developed for the shape-selective synthesis of less-common Au nanostructures, including flower, sphere, dendrite, rod, sheet, and cabbage onto the aligned MWCNTs at room temperature. Especially, among all the synthesis methods for Au nanocrystals, this is the first report using electrochemical technique to synthesize wide variety shapes of gold nanostructures (GNs) onto the aligned MWCNTs. The morphology of electrodeposited Au nanostructures was controlled by adjustment of the deposition time and potential, the number of potential cycles, the kind of deposition bath, and electrodeposition method. Transmission electron microscopy and field-emission scanning electron microscopy were used to characterize the products. Cyclic voltammograms showed that the MWCNT/Ta electrodes modified with GNs have higher sensitivity compared to the unmodified electrodes in the presence of Fe2+/Fe3+ redox couple. These kinds of aligned-CNT/Au nanostructure hybrid materials introduced by these efficient and simple electrochemical methods could lead to the development of a new generation device for ultrasensitive catalytic and biological application.