Electrochemically Activated CNT Sheet as a Cathode for Zn-CO2 Batteries.

High demand for electrochemical storage devices is increasing the need for high-performance batteries. A Zn-CO2 battery offers a promising solution for CO2 reduction as well as energy storage applications. For this study, a Zn-CO2 battery was fabricated using a Carbon Nanotube (CNT) sheet as a cathode and a Zn plate as an anode. The electrochemical activation technique was used to increase the surface area of the CNT electrode by roughly 4.5 times. Copper (Cu) as a catalyst was then deposited onto the activated CNT electrode using electrodeposition method and different Cu loadings were investigated to optimize CO2 reduction. The final assembled Zn-CO2 battery has a 1.6 V output voltage at a current density of 0.063 mA/cm2, which is higher than most devices reported in the literature. This study demonstrates the importance of activation process which enabled more catalyst loading on the cathode resulted in additional active sites for electroreduction process. This paper presents the activated CNT sheet as a promising cathode material for Zn-CO2 batteries.

Biodegradable Zwitterionic Polymer Coatings for Magnesium Alloy Stents.

Degradable metallic stents, most commonly composed of Mg-based alloys, are of interest as an alternative to traditional metallic stents for application in cardiac and peripheral vasculature. Two major design challenges with such stents are control of the corrosion rate and acute presentation of a nonthrombogenic surface to passing blood. In this study, several types of sulfobetaine (SB)-bearing biodegradable polyurethanes were developed and assessed as physical, chemical, and combination-type coatings for a model degradable Mg alloy, AZ31. For physical coatings, poly(ester sulfobetaine)urethane ureas, PESBUUs were synthesized using variable monomers that allowed the incorporation of a varying extent of carboxyl groups. Introduction of the carboxyl groups was associated with faster polymer degradation time. Simple physical coating of PESBUUs reduced macro- and microscopic thrombogenic deposition together with good stability of the coating attachment compared to a control coating of polylactic- co-glycolic acid. For PESBUUs incorporating carboxyl groups (PESBUUs-COOH), these groups could be converted to siloxane groups (PESBUUs-Si), thus creating polymers that could be surface reacted with the oxidized or phytic acid treated AZ31 surface. Chemical (silanization) attachment of these polymers reduced underlying alloy corrosion rates, but following the salination reaction with physical coating most reduced corrosion rates and protected the surface better from the consequences of oxidation occurring under the coating, such as blistering. The application of a multilayered coating approach using a sulfobetaine-based biodegradable elastomer thus offers options for degradable metallic stent design where thromboresistance is desired in combination with a means to control both polymeric coating degradation rates and underlying alloy corrosion rates.

Electrically heatable carbon nanotube point-of-use filters for effective separation and in-situ inactivation of Legionella pneumophila.

Despite municipal chlorination and secondary disinfection, opportunistic waterborne pathogens (e.g., Legionella spp.) persist in public and private water distribution systems. As a potential source of healthcare-acquired infections, this warrants development of novel pathogen removal and inactivation systems. In this study, electrically heatable carbon nanotube (CNT) point-of-use (POU) filters have been designed to remove and inactivate Legionella pneumophila in water. The CNT/polymer composite membranes effectively removed Legionella (> 99.99%) (i.e., below detection limit) and were able to inactive them on the membrane surface at 100% efficiency within 60 s using ohmic heating at 20 V. The novel POU filters could be used as a final barrier to provide efficient rejection of pathogens and thereby simultaneously eliminate microorganisms in public and private water supplies.

Carbon Nanotube Thread Electrochemical Cell: Detection of Heavy Metals.

In this work, all three electrodes in an electrochemical cell were fabricated based on carbon nanotube (CNT) thread. CNT thread partially insulated with a thin polystyrene coating to define the microelectrode area was used as the working electrode; bare CNT thread was used as the auxiliary electrode; and a micro quasi-reference electrode was fabricated by electroplating CNT thread with Ag and then anodizing it in chloride solution to form a layer of AgCl. The Ag|AgCl coated CNT thread electrode provided a stable potential comparable to the conventional liquid-junction type Ag|AgCl reference electrode. The CNT thread auxiliary electrode provided a stable current, which is comparable to a Pt wire auxiliary electrode. This all-CNT thread three electrode cell has been evaluated as a microsensor for the simultaneous determination of trace levels of heavy metal ions by anodic stripping voltammetry (ASV). Hg2+, Cu2+, and Pb2+ were used as a representative system for this study. The calculated detection limits (based on the 3σ method) with a 120 s deposition time are 1.05, 0.53, and 0.57 nM for Hg2+, Cu2+, and Pb2+, respectively. These electrodes significantly reduce the dimensions of the conventional three electrode electrochemical cell to the microscale.

Flexible Micro-Supercapacitor Based on Graphene with 3D Structure.

Flexible micro-supercapacitors (MSCs) are constructed by 3D graphene from chemical vapor deposition. Without using any binder or metal current collector, the as-prepared 3D graphene MSC exhibits good flexibility, excellent cyclic life, and high areal capacitance of 1.5 mF cm-2 at a scan rate of 10 V s-1 . The electrochemical performance is further improved by oxygen plasma functionalization.

Heatable carbon nanotube composite membranes for sustainable recovery from biofouling.

Membrane filtration is one of the most reliable methods for water treatment. However, wider application is limited due to biofouling caused by accumulation of microorganisms on the membrane surface. This report details a heatable carbon nanotube composite membrane with self-cleaning properties for sustainable recovery from biofouling. Microfiltration polycarbonate/carbon-nanotubes hybrid membranes were fabricated using drawable nanotubes that maintained the porosity and provided electrical conductivity to the membrane. Less than 25 V potential and 2-3 W power increase membrane temperature to 100°C in ~10 s. This temperature is above what most microbial life, bacteria and viruses can handle. When this membrane was employed, filtered Escherichia coli collected on its surface were successfully annihilated within 1 min. Ohmic heating of this membrane could be an effective solution to combat biofouling and complications associated with membrane-based filtration. This is a novel and highly desirable approach to combat biofouling, due to its simplicity and economic advantage.

Optically transparent carbon nanotube film electrode for thin layer spectroelectrochemistry.

Carbon nanotube (CNT) film was evaluated as an optically transparent electrode (OTE) for thin layer spectroelectrochemistry. Chemically inert CNT arrays were synthesized by chemical vapor deposition (CVD) using thin films of Fe and Co as catalysts. Vertically aligned CNT arrays were drawn onto a quartz slide to form CNT films that constituted the OTE. Adequate conductivity and transparency make this material a good OTE for spectroelectrochemistry. These properties could be varied by the number of layers of CNTs used to form the OTE. Detection in the UV/near UV region down to 200 nm can be achieved using these transparent CNT films on quartz. The OTE was characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, UV-visible spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and thin layer spectroelectrochemistry. Ferricyanide, tris(2,2'-bipyridine) ruthenium(II) chloride, and cytochrome c were used as representative redox probes for thin layer spectroelectrochemistry using the CNT film OTE, and the results correlated well with their known properties. Direct electron transfer of cytochrome c was achieved on the CNT film electrode.

Inverse-Ordered Fabrication of Free-Standing CNT Sheets for Supercapacitor.

Free-standing thin carbon nanotube (CNT) sheets are challenging to handle and control for device fabrication. In this paper, we report on the inverse-ordered fabrication method from thick CNT sheets to thin free-standing CNT sheets. As proof of the concept, thin CNT sheets for a supercapacitor were fabricated from 200 thick layers. The results show that the thin CNT sheet was electrochemically stable and had enhanced capacitive performance. The smaller the number of layers is, the larger the specific capacitances we have (from 10.10 F g(-1) to 51.37 F g(-1)). Energy and power density were increased from 0.50 to 2.57 Wh kg(-1) and from 0.33 to 2.31 kW kg(-1), respectively. This simple and scalable inverse-ordered method is capable to fabricate CNT sheets in various forms, allowing fast trials on various applications.

Modified 3D Graphene for Sensing and Electrochemical Capacitor Applications.

Less defective, nitrogen-doped 3-dimensional graphene (N3DG) and defect-rich, nitrogen-doped 3-dimensional graphene (N3DG-D) were made by the thermal CVD (Chemical Vapor Deposition) process via varying the carbon precursors and synthesis temperature. These modified 3D graphene materials were compared with pristine 3-dimensional graphene (P3DG), which has fewer defects and no nitrogen in its structure. The different types of graphene obtained were characterized for morphological, structural, and compositional assessment through Scanning Electron Microscopy (SEM), Raman Spectroscopy, and X-ray Photoelectron Spectroscopy (XPS) techniques. Electrodes were fabricated, and electrochemical characterizations were conducted to evaluate the suitability of the three types of graphene for heavy metal sensing (lead) and Electric Double-Layer Capacitor (EDLC) applications. Initially, the various electrodes were treated with a mixture of 2.5 mM Ruhex (Ru (NH3)6Cl3 and 25 mM KCl to confirm that all the electrodes underwent a reversible and diffusion-controlled electrochemical process. Defect-rich graphene (N3DG-D) revealed the highest current density, followed by pristine (P3DG) and less-defect graphene (N3DG). Further, the three types of graphene were subjected to a sensing test by square wave anodic stripping voltammetry (SWASV) for lead detection. The obtained preliminary results showed that the N3DG material provided a great lead-sensing capability, detecting as little as 1 µM of lead in a water solution. The suitability of the electrodes to be employed in an Electric Double-Layer Capacitor (EDLC) was also comparatively assessed. Electrochemical characterization using 1 M sodium sulfate electrolyte was conducted through cyclic voltammetry and galvanostatic charge-discharge studies. The voltammogram and the galvanostatic charge-discharge (GCD) curves of the three types of graphene confirmed their suitability to be used as EDLC. The N3DG electrode proved superior with a gravimetric capacitance of 6.1 mF/g, followed by P3DG and N3DG, exhibiting 1.74 mF/g and 0.32 mF/g, respectively, at a current density of 2 A/g.

Nanoimprint Lithography for Next-Generation Carbon Nanotube-Based Devices.

This research reports the development of 3D carbon nanostructures that can provide unique capabilities for manufacturing carbon nanotube (CNT) electronic components, electrochemical probes, biosensors, and tissue scaffolds. The shaped CNT arrays were grown on patterned catalytic substrate by chemical vapor deposition (CVD) method. The new fabrication process for catalyst patterning based on combination of nanoimprint lithography (NIL), magnetron sputtering, and reactive etching techniques was studied. The optimal process parameters for each technique were evaluated. The catalyst was made by deposition of Fe and Co nanoparticles over an alumina support layer on a Si/SiO2 substrate. The metal particles were deposited using direct current (DC) magnetron sputtering technique, with a particle ranging from 6 nm to 12 nm and density from 70 to 1000 particles/micron. The Alumina layer was deposited by radio frequency (RF) and reactive pulsed DC sputtering, and the effect of sputtering parameters on surface roughness was studied. The pattern was developed by thermal NIL using Si master-molds with PMMA and NRX1025 polymers as thermal resists. Catalyst patterns of lines, dots, and holes ranging from 70 nm to 500 nm were produced and characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Vertically aligned CNTs were successfully grown on patterned catalyst and their quality was evaluated by SEM and micro-Raman. The results confirm that the new fabrication process has the ability to control the size and shape of CNT arrays with superior quality.

Three-Dimensional Graphene Sheet-Carbon Veil Thermoelectric Composite with Microinterfaces for Energy Applications.

Over the years, various processing techniques have been explored to synthesize three-dimensional graphene (3DG) composites with tunable properties for advanced applications. In this work, we have demonstrated a new procedure to join a 3D graphene sheet (3DGS) synthesized by chemical vapor deposition (CVD) with a commercially available carbon veil (CV) via cold rolling to create 3DGS-CV composites. Characterization techniques such as scanning electron microscopy (SEM), Raman mapping, X-ray diffraction (XRD), electrical resistance, tensile strength, and Seebeck coefficient measurements were performed to understand various properties of the 3DGS-CV composite. Extrusion of 3DGS into the pores of CV with multiple microinterfaces between 3DGS and the graphitic fibers of CV was observed, which was facilitated by cold rolling. The extruded 3D graphene revealed pristine-like behavior with no change in the shape of the Raman 2D peak and Seebeck coefficient. Thermoelectric (TE) power generation and photothermoelectric responses have been demonstrated with in-plane TE devices of various designs made of p-type 3DGS and n-type CV couples yielding a Seebeck coefficient of 32.5 µV K-1. Unlike various TE materials, 3DGS, CV, and the 3DGS-CV composite were very stable at high relative humidity. The 3DGS-CV composite revealed a thin, flexible profile, good moisture and thermal stability, and scalability for fabrication. These qualities allowed it to be successfully tested for temperature monitoring of a Li-ion battery during charging cycles and for large-area temperature mapping.

Manufacturing Scalable Carbon Nanotube-Silicone/Kevlar Fabrics.

Carbon nanotube (CNT) hybrid composites were formed by combining a CNT and silicone elastomer solution with Kevlar yarn, Kevlar fabric, and Kevlar veil materials. The integration of a CNT-silicone matrix with Kevlar yarn and fabric materials produced a composite with moderate electrical and thermal conductivity due to CNT fabric combined with the strength of Kevlar fabric or yarn. In the material synthesis, a notable difficulty was that the CNT-silicone did not bond strongly to the Kevlar. The composites passed the Vertical Flame Test ASTM D6413 and the Forced Air Oven Test NFPA 1971. These hybrid composites can have multiple applications in areas requiring favorable conductivity, strength, and flame and heat resistance. The application areas include firefighter apparel, military equipment, conductive/smart structures, and flexible electronics. The synthesis process used to manufacture CNT-silicone/Kevlar composites yielded composite sheets with an area of 2250 cm2. The process is scalable and customizable for the synthesis of CNT composites with tailored properties. Improvements in the bonding of CNT-silicone to Kevlar are being investigated.

Carbon Hybrid Materials-Design, Manufacturing, and Applications.

Carbon nanotubes (CNTs) have extraordinary properties and are used for applications in various fields of engineering and research. Due to their unique combination of properties, such as good electrical and thermal conductivity and mechanical strength, there is an increasing demand to produce CNTs with enhanced and customized properties. CNTs are produced using different synthesis methods and have extraordinary properties individually at the nanotube scale. However, it is challenging to achieve these properties when CNTs are used to form macroscopic sheets, tapes, and yarns. To further improve the properties of macroscale forms of CNTs, various types of nanoparticles and microfibers can be integrated into the CNT materials. The nanoparticles and microfibers can be chosen to selectively enhance the properties of CNT materials at the macroscopic level. In this paper, we propose a technique to manufacture carbon hybrid materials (CHMs) by combining CNT non-woven fabric (in the form of sheets or tapes) with microfibers to form CNT-CF hybrid materials with new/improved properties. CHMs are formed by integrating or adding nanoparticles, microparticles, or fibers into the CNT sheet. The additive materials can be incorporated into the synthesis process from the inlet or the outlet of the reactor system. This paper focuses on CHMs produced using the gas phase pyrolysis method with microparticles/fibers integrated at the outlet of the reactor and continuous microfiber tapes integrated into the CNT sheet at the outlet using a tape feeding machine. After synthesis, characterizations such as microscopy and thermogravimetric analysis were used to study the morphology and composition of the CNTs, and examples for potential applications are discussed in this paper.

Boosting Thermoelectric Power Factor of Carbon Nanotube Networks with Excluded Volume by Co-Embedded Microparticles.

Carbon nanotube (CNT) networks embedded in a polymer matrix have been extensively studied as a flexible thermoelectric transport medium over the recent years. However, their power factor has been largely limited by the relatively inefficient tunneling transport at junctions between CNTs and the low-density conducting channels throughout the networks. This work demonstrates that significant power factor enhancements can be achieved by adding electrically insulating microscale particles in three-dimensional CNT networks embedded in the polymer matrix. When silica particles of a few µm diameters were co-embedded in single-walled CNT (SWCNT)-polydimethylsiloxane (PDMS) composites, both the electrical conductivity and the Seebeck coefficient were simultaneously enhanced, thereby boosting the power factor by more than a factor of six. We found that the silica microparticles excluded a large volume of the composite from the access of CNTs and caused CNT networks to form around them with the polymer as a binder, resulting in improved network connectivity and alignment of CNTs. Our theoretical calculations based on junction tunneling transport for three-dimensional CNT networks show that the significant power factor enhancement can be attributed to the enhanced tunneling with reduced junction distance between CNTs. Additional power factor enhancement by a factor of three was achieved by sample compression, which further reduced the mean junction distance to enhance tunneling but also reduced the geometric factor at the same time, limiting the enhancement of electrical conductivity.

Hydrogen Nanometrology in Advanced Carbon Nanomaterial Electrodes.

A comparative experimental study between advanced carbon nanostructured electrodes, in similar hydrogen uptake/desorption conditions, is investigated making use of the recent molecular beam-thermal desorption spectrometry. This technique is used for monitoring hydrogen uptake and release from different carbon electrocatalysts: 3D-graphene, single-walled carbon nanotube networks, multi-walled carbon nanotube networks, and carbon nanotube thread. It allows an accurate determination of the hydrogen mass absorbed in electrodes made from these materials, with significant enhancement in the signal-to-noise ratio for trace hydrogen avoiding recourse to ultra-high vacuum procedures. The hydrogen mass spectra account for the enhanced surface capability for hydrogen adsorption in the different types of electrode in similar uptake conditions, and confirm their enhanced hydrogen storage capacity, pointing to a great potential of carbon nanotube threads in replacing the heavier metals or metal alloys as hydrogen storage media.

Chlorosulfonic Acid Stretched Carbon Nanotube Sheet for Flexible and Low-Voltage Heating Applications.

The carbon nanotube (CNT) is celebrated for its electrothermal property, which indicates the capability of a material to transform electrical energy into heat due to the Joule effect. The CNT nanostructure itself, as a one-dimensional material, limits the electron conduction path, thereby creating a unique heating phenomenon. In this work, we explore the possible correlation between CNT alignment in sheets and heating performance. The alignment of carbon nanotubes is induced by immersion and stretching in chlorosulfonic acid (CSA) solution. The developed CSA-stretched CNT sheet demonstrated excellent heating performance with a fast response rate of 6.5 °C/s and reached 180 °C in less than 30 s under a low voltage of 2.5 V. The heating profile of the stretched CNT sheet remained stable after bending and twisting movements, making it a suitable heating material for wearable devices, heatable smart windows, and in de-icing or defogging applications. The specific strength and specific conductance of the CSA-stretched CNT sheet also increased five- and two-fold, respectively, in comparison to the pristine CNT sheet.

CVD Synthesis of 3D-Shaped 3D Graphene Using a 3D-Printed Nickel-PLGA Catalyst Precursor.

Earlier, various attempts to develop graphene structures using chemical and nonchemical routes were reported. Being efficient, scalable, and repeatable, 3D printing of graphene-based polymer inks and aerogels seems attractive; however, the produced structures highly rely on a binder or an ice support to stay intact. The presence of a binder or graphene oxide hinders the translation of the excellent graphene properties to the 3D structure. In this communication, we report our efforts to synthesize a 3D-shaped 3D graphene (3D2G) with good quality, desirable shape, and structure control by combining 3D printing with the atmospheric pressure chemical vapor deposition (CVD) process. Direct ink writing has been used in this work as a 3D-printing technique to print nickel powder-PLGA slurry into various shapes. The latter has been employed as a catalyst for graphene growth via CVD. Porous 3D2G with high purity was obtained after etching out the nickel substrate. The conducted micro CT and 2D Raman study of pristine 3D2G revealed important features of this new material. The interconnected porous nature of the obtained 3D2G combined with its good electrical conductivity (about 17 S/cm) and promising electrochemical properties invites applications for energy storage electrodes, where fast electron transfer and intimate contact with the active material and with the electrolyte are critically important. By changing the printing design, one can manipulate the electrical, electrochemical, and mechanical properties, including the structural porosity, without any requirement for additional doping or chemical postprocessing. The obtained binder-free 3D2G showed a very good thermal stability, tested by thermo-gravimetric analysis in air up to 500 °C. This work brings together two advanced manufacturing approaches, CVD and 3D printing, thus enabling the synthesis of high-quality, binder-free 3D2G structures with a tailored design that appeared to be suitable for multiple applications.

Preliminary study on modelling, fabrication by photo-chemical etching and in vivo testing of biodegradable magnesium AZ31 stents.

Magnesium metal (Mg) is a promising material for stent applications due to its biocompatibility and ability to be resorbed by the body. Manufacturing of stents by laser cutting has become an industry standard. Our alternative approach uses photo-chemical etching to transfer a pattern of the stent onto a Mg sheet. In this study, we present three stages of creating and validating a stent prototype, which includes design and simulation using finite element analysis (FEA), followed by fabrication based on AZ31 alloy and, finally, in vivo testing in peripheral arteries of domestic pigs. Due to the preliminary character of this study, only six stents were implanted in two domestic farm pigs weighing 25-28 kg and they were evaluated after 28 days, with an interim follow-up on day 14. The left and right superficial femoral, the left iliac, and the right renal artery were selected for this study. The diameters of the stented artery segments were evaluated at the time of implantation, on day 14 and then, finally, on day 28, by quantitative vessel analysis (QVA) using fluoroscopic imaging. Optical Coherence Tomography (OCT) imaging displayed some malposition, breaks, stacking, and protrusion into the lumen at the proximal, distal, and mid-sections of the stented arteries. The stents degraded with time, but simultaneously became embedded in the intima. After 28 days, the animals were euthanized, and explanted vessels were fixed for micro-CT imaging and histology studies. Micro-CT imaging revealed stent morphological and volumetric changes due to the in-body degradation. An in vivo corrosion rate of 0.75 mm/year was obtained by the CT evaluation. The histology suggested no-life threatening effects, although moderate injury, inflammation, and endothelialization scores were observed.

Regulation of functional groups on graphene quantum dots directs selective CO2 to CH4 conversion.

A catalyst system with dedicated selectivity toward a single hydrocarbon or oxygenate product is essential to enable the industrial application of electrochemical conversion of CO2 to high-value chemicals. Cu is the only known metal catalyst that can convert CO2 to high-order hydrocarbons and oxygenates. However, the Cu-based catalysts suffer from diverse selectivity. Here, we report that the functionalized graphene quantum dots can direct CO2 to CH4 conversion with simultaneous high selectivity and production rate. The electron-donating groups facilitate the yield of CH4 from CO2 electro-reduction while electron-withdrawing groups suppress CO2 electro-reduction. The yield of CH4 on electron-donating group functionalized graphene quantum dots is positively correlated to the electron-donating ability and content of electron-donating group. The graphene quantum dots functionalized by either -OH or -NH2 functional group could achieve Faradaic efficiency of 70.0% for CH4 at -200 mA cm-2 partial current density of CH4. The superior yield of CH4 on electron-donating group- over the electron-withdrawing group-functionalized graphene quantum dots possibly originates from the maintenance of higher charge density of potential active sites (neighboring C or N) and the interaction between the electron-donating group and key intermediates. This work provides insight into the design of active carbon catalysts at the molecular scale for the CO2 electro-reduction.

Self-aligned nanogaps on multilayer electrodes for fluidic and magnetic assembly of carbon nanotubes.

A self-aligned nanogap between multiple metal layers has been developed using a new controlled undercut and metallization technique (CUMT), and practically applied for self-assembly of individual carbon nanotubes (CNTs) over the developed nanogap. This new method allows conventional optical lithography to fabricate nanogap electrodes and self-aligned patterns with nanoscale precision. The self-aligned nickel (Ni) pattern on the nanogap electrode works as an assembly spot where the residual iron (Fe) catalyst at the end of the CNT is magnetically captured. The captured CNT is forced to be aligned parallel to the flow direction by fluidic shear force. The combined forces of magnetic attraction and fluidic alignment provide massive self-assembly of CNTs at target positions. Both multiwalled nanotubes (MWNTs) and single walled nanotubes (SWNTs) were successfully assembled over the nanogap electrodes, and their electrical characteristics were fully characterized. The CNTs self-assembled on the developed electrodes with a nanogap and showed a very reliable and reproducible current-voltage (I-V) characteristic. The method developed in this work can envisage the mass fabrication of individual CNT-assembled devices which can be applied to nanoelectronic devices or nanobiosensors.