Compositional Control as the Key for Achieving Highly Efficient OER Electrocatalysis with Cobalt Phosphates Decorated Nanocarbon Florets.

Compositional interplay of two different cobalt phosphates (Co(H2 PO4 )2 ; Co-DP and Co(PO3 )2 ; Co-MP) loaded on morphologically engineered high surface area nanocarbon leads to an increased electrocatalytic efficiency for oxygen evolution reaction (OER) in near neutral conditions. This is reflected as significant reduction in the onset overpotential (301 mV) and enhanced current density (30 mA cm-2 @ 577 mV). In order to achieve uniform surface loading, organic-soluble thermolabile cobalt-bis(di-tert-butylphosphate) is synthesized in situ inside the nanocarbon matrix and subsequently pyrolyzed at 150 °C to produce Co(H2 PO4 )2 /Co(PO3 )2 (80:20 wt%). Annealing this sample at 200 or 250 °C results in the redistribution of the two phosphate systems to 55:45 or 20:80 (wt%), respectively. Detailed electrochemical measurements clearly establish that the 55:45 (wt%) sample prepared at 200 °C performs the best as a catalyst, owing to a relay mechanism that enhances the kinetics of the 4e- transfer OER process, which is substantiated by micro-Raman spectroscopic studies. It is also unraveled that the engineered nanocarbon support simultaneously enhances the interfacial charge-transfer pathway, resulting in the reduction of onset overpotential, compared to earlier investigated cobalt phosphate systems.

Ultra-sensitive gas phase detection of 2,4,6-trinitrotoluene by non-covalently functionalized graphene field effect transistors.

The high energy density (4.2 MJ kg-1) and low vapour pressure (7.2 × 10-9 atm) of chemical explosives such as TNT (2,4,6-trinitrotoluene) pose a grave security risk demanding immediate attention. Detection of such hazardous and highly challenging chemicals demands specific, ultra-sensitive and rapid detection platforms that can concomitantly transduce the signal as an electrical readout. Although chemo-sensitive strategies have been investigated, the majority of them are restricted to detecting TNT from solutions and are therefore not implementable in real-time, on-field situations. Addressing this demand, we report an ultra-sensitive (parts-per-billion) and rapid (∼40 s) detection platform for TNT based on non-covalently functionalized graphene field effect transistors (GFETs). This multi-parametric GFET detector exhibits a reliable and specific modulation in its Dirac point upon exposure to TNT in the vapour phase. The chemical specificity provided by 5-(4-hydroxyphenyl)-10,15,20-tri(p-tolyl) zinc porphyrin (ZnTTPOH) is synergistically combined with the high surface sensitivity of graphene through a non-covalent functionalization approach to realise p-doped GFETs (Zn-GFETs). Such a FET platform exhibits extremely sensitive shifts in Dirac point (ΔDP) that correlate with the number of nitro groups present in the analyte. Analytes with mono-, di-, and tri-nitro substituted aromatic molecules exhibit distinctly different ΔDP, leading to unprecedented specificity towards TNT. Additionally, the Dirac point of Zn-GFETs is invariant for common and potential interferons such as acetone and 2-propanol (perfume emulsifiers) thereby validating their practical applicability. Furthermore, the ΔDP is also manifested as changes in the contact potential of GFETs, indicating that sub-monolayer coverage of ZnTTPOH is sufficient to modulate the transfer characteristics of GFETs over an area 1000 times larger than the dopant dimensions. Specifically, ZnTTPOH-functionalized GFETs exhibit p-doped behaviour with positive ΔDP with respect to pristine GFETs. Such p-doped Zn-GFETs undergo selective charge-transfer mediated interactions with TNT resulting in enhanced electron withdrawal from Zn-GFETs. Thus the ΔDP shifts to a higher positive gate voltage leading to the dichotomous combination of the highest signal generation (1.2 × 1012 V mol-1) with ppb level molecular sensitivity. Significantly, the signal generated due to TNT is 105 times higher in magnitude compared to other potential interferons. The signal reliability is established in cross-sensitivity measurements carried out with a TNT-mDNB (1 : 10 molar ratio) mixture pointing to high specificity for immediate applications under atmospherically relevant conditions pertaining to homeland security and global safety.

Interplay of Size and Magnetic Effects in Electrocatalytic Water Oxidation Activity of Sub-10†nm NiOx Supported Porous Hard-Carbons.

This report describes a systematic approach for precise engineering of a catalyst-metal oxide interface through combining complementary approaches of chemical vapor deposition and atomic layer deposition. Specifically, Chemical Vapor Deposition (CVD) fabricated nanostructured hard-carbon framework (NCF) is employed as synergistic support for precise deposition of NiOx particles through Atomic Layer Deposition (ALD). The three variants of NCF-NiOx system (dimensions ranging from 3-12 nm, surface coverage ranging from 0.14 %-2 %) achieved exhibit unique electrocatalytic water oxidation activities, that are further strongly influenced by an external magnetic field (Hext). This confluence of size engineering and associated magnetic field effects interplay to produce the largest lowering in Rct at Hext=200 mT. A comprehensive analysis of electrocatalytic parameters including the Tafel slope and double layer capacitance establishes further insights on co-relation of size effect and magnetic properties to understand the role of nanocarbon supported transition metal oxides in water electrolysis.

Phonon-Engineered Hard-Carbon Nanoflorets Achieving Rapid and Efficient Solar-Thermal Based Water Evaporation and Space-Heating.

Generation and utilization of green heat produced from solar energy demand broadband absorbers with the elusive combination of strong phonon-driven photon thermalization and, contrastingly, weak phonon-lattice thermal conductivity. Here, we report a new class of porous, nanostructured hard-carbon florets (NCFs) consisting of isotropically assembled conical microcavities for greater light entrapment and efficient broad-band absorption (95% over 250-2500 nm). Resembling marigolds, the NCF exhibits short-range graphitic order that promotes instantaneous and efficient solar-thermal conversion (ηSTC = 87%) while exhibiting long-range intrinsic disorder providing low thermal conductivity (1.5 W m-1 K-1) to minimize thermal loss (13%). Solution processable NCF coatings on arbitrarily substrates (filter paper, terracotta, Cu and Al tubes) generate surface temperature of 400 ± 2 K and exhibit high thermal effusance (519 W s0.5 m-2 K-1) to achieve highest combination of (a) rate of solar-driven interfacial water evaporation (Rw = 5.4 kg m-2 h-1, 2 sun), (b) solar-vapor conversion efficiency (ηSVC = 186%), and (c) ηSTC (87%) among known materials. Such robust performance is retained for beyond 30 days of continuous operation and under different solar power (1 sun to 5 sun). Furthermore, active space heating (outlet air temperature = 346 ± 3 K) using NCF coatings is demonstrated.

Exploiting the Synergism of a Carbon-Catalyst Interface to Achieve Magneto-Electrocatalytic Overall Water Splitting at 2.197 V.

The desire to electrolyze water at low energy and high kinetics for achieving rapid H2 production forms the holy grail for the paradigm shift to a sustainable H2-driven economy. While alkaline electrolysis is preferred due to the use of earth-abundant catalysts, its sluggish kinetics and high overpotential are the persistent challenges. Addressing this, we demonstrate the coupling of an externally applied magnetic field (Hext) to a synergistically designed interface of nanostructured carbon floret with antiferromagnetic NiO nanoflakes that act in unison to achieve rapid hydrogen generation (6.3 N m3 h-1 W-1) that is comparable with existing technologies. Specifically, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials are simultaneously reduced by 10 and 7%, respectively, under the influence of a weak fridge magnet (Hext = 200 mT). Consequently, ∼11% improvement in the energy efficiency is observed with a 21% reduced cell voltage for overall water splitting. The stability of the system is demonstrated over a prolonged lifetime of ∼95 h. This performance enhancement with Hext for both HER and OER is explained in terms of improved kinetic facility for the reaction and lower resistance of charge transfer pathway. Moreover, the electrocatalyst is seen to retain the improved performance for prolonged usage (∼3 h) even after the removal of the Hext, and hence, it provides an energy-efficient hydrogen and oxygen generation pathway.

Joule Heating-Driven Transformation of Hard-Carbons to Onion-like Carbon Monoliths for Efficient Capture of Volatile Organic Compounds.

Soft graphitizable carbon-based multifunctional nanomaterials have found versatile applications ranging from energy storage to quantum computing. In contrast, their hard-carbon analogues have been poorly investigated from both fundamental and application-oriented perspectives. The predominant challenges have been (a) the lack of approaches to fabricate porous hard-carbons and (b) their thermally nongraphitizable nature, leading to inaccessibility for several potential applications. In this direction, we present design principles for fabrication of porous hard-carbon-based nanostructured carbon florets (NCFs) with a highly accessible surface area (∼936 m2/g), rivalling their soft-carbon counterparts. Subjecting such thermally stable hard-carbons to a synergistic combination of an electric field and Joule heating drives their transformation to free-standing macroscopic monoliths composed of onion-like carbons (OLCMs). This represents the first such structural transformation observed in sp2-based hard-carbon NCFs to sp2-networked OLCMs. Micro-Raman spectroscopy establishes the simultaneous increase in the intensity of D-, 2D-, and D + G-bands at 1341, 2712, and 2936 cm-1 and is correlated to the reorganization in the disordered graphitic domains of NCFs to curved concentric nested spheres in OLCMs. This therefore completely precludes the formation of a nanodiamond core that has been consistently observed in all previously reported OLCs. The Joule heating-driven formation of OLCMs is accompanied by ∼5700% enhancement in electrical conductivity that is brought about by the fusion of outermost graphitic shells of OLCs to result in monolithic OLC structures (OLCMs). The porous and inter-networked OLCMs exhibit an excellent adsorption-based capture of volatile organic compounds such as toluene at high efficiencies (∼99%) over a concentration range (0.22-1.86 ppm) that is relevant for direct applications such as smoke filters in cigarettes.

Electric-Field-Induced Solid-Gas Interfacial Chemical Reaction in Carbon Nanotube Ensembles: Route toward Ultra-sensitive Gas Detectors.

The electric field at the sharp pointed tips of single wall carbon nanotube ensembles has been utilized to kinetically accelerate hitherto unobserved chemical reactions at the heterogeneous solid-gas interfaces. The principle of ″action-of-points″ drives specific chemical reactions between the defect sites of single wall carbon nanotubes (CNTs) and ppb levels of gaseous hydrogen sulfide. This is manifested as changes in the electrical conductivity of the conductive CNT-ensemble (cCNT) and visually tracked as enthalpic modulations at the site of the reaction through infrared thermometry. Importantly, the principle has been observed for a variety of analytes such as NH3, H2O, and H2S, leading to distinctly correlatable changes in reactivity and conductivity changes. Theoretical calculations based on the density functional theory in the presence and absence of applied electric field reveal that the applied electric field activates the H2S gas molecules by charge polarization, yielding favorable energetics. These results imply the possibility of carrying out site-specific chemical modifications for nanomaterials and also provide transformative opportunities for the development of miniaturized e-nose-based gas analyzers.

Design Principles for Manipulating Electrochemical Interfaces in Solid-State Supercapacitors for Wearable Applications.

Storage and delivery of electrical energy form the heart of the rapidly expanding domain of wearable electronics, with applications ranging from point-of-care medical diagnostics to Internet-of-Things (IoT). Solid-state, electrochemical, double-layer-based supercapacitive energy storage devices, with high power density, ability to interface with intermittent energy harvesters, long lifetime, and cyclability, offer attractive possibilities for self-sustaining power sources in such portable applications. This mini-review highlights the need for a multipronged approach involving (a) development of materials for electrodes and electrolyte and (b) utilizing the right kind of design principles, processing techniques, and fabrication approaches to (c) achieve seamless all-solid electrode-electrolyte interfaces providing (d) facile integration onto wearable platforms. Importantly, a comprehensive figure-of-merit (FOM) accounting for both the electrochemical performance and the mechanical robustness of flexible supercapacitors is proposed. This is expected to facilitate uniform comparison of performance across devices differing in their design approaches and materials. Finally, new operando and in situ techniques for probing and understanding such all-solid interfaces are presented. The iterative cycle of scientific understanding, furthering technological advancements, seeks to provide future directions for achieving mechanically robust supercapacitors with enhanced energy density and power density for wearable and portable applications.

Scalable approach towards specific and ultrasensitive cation sensing under harsh environmental conditions by engineering the analyte-transducer interface.

Affordable and high-performing sensing platforms are becoming increasingly critical for sustainable environmental monitoring and medical diagnostics. Such miniaturized and point-of-care sensing platforms need to overcome the fundamental tradeoff between ultrahigh sensitivity and specificity while retaining the dynamic concentration range and robustness of operation. Therefore, designing scalable and robust sensors poses an escalating and immediate demand in a rapidly automated society. Addressing this demand, we demonstrate a cable-type electrochemical sensing platform exhibiting rapid (10 s), extremely reliable (RSD <5%) and ultrahigh sensitivity (ppb levels) towards K+, Cd2+ and Hg2+ found in complex biofluids such as human perspiration and effluent water. The sensor delivers quantifiable performance even with 10 µL of analyte without any requirement of purification or preconcentration and thereby overcomes an important bottleneck for on-field diagnostics. The backbone of the sensor consists of single-walled carbon nanotubes (CNTs) that are conformally coated on affordable cellulose yarns to form ideally non-Faradaic, electrically conductive, capacitive electrodes (CNT-thread). Subsequent coaxial coating of such CNT-threads with an appropriate ionophore membrane (IM) realizes the working electrode exhibiting uniformity in the surface coverage of the ionophore leading to reliable and directly quantifiable signals. Furthermore, we show that the extensive CNT-thread-IM interface is critical to achieve ultrahigh sensitivity and robust operability. Importantly, the design approach adopted is universal and scalable for a range of cations such as K+, Hg2+ and Cd2+. Thus, the sensor delivers ultrasensitive detection of K+ from very low volumes (10 µL) of human perspiration that contains a wide range of other ions (Cu2+, Zn2+, Cd2+, Fe2+, NO3 -, Cl-) at 1000-fold higher ionic strength along with bioinorganic suspended matter (dead cells, organelles). This eliminates any sample treatment or preconcentration requirements thereby overcoming a major obstacle for point-of-care applications. Furthermore, both multicomponent and multivariate analyses are demonstrated with the sensing device targeting portable and wearable applications.

Non-Stoichiometry Induced Exsolution of Metal Oxide Nanoparticles via Formation of Wavy Surfaces and their Enhanced Electrocatalytic Activity: Case of Misfit Calcium Cobalt Oxide.

Most heterogeneous catalytic reactions demand high density and yet spatially separated nanoparticles that are strongly anchored on the oxide surfaces. Such nanoparticles can be deposited or synthesized in situ via nonstoichiometric methods. To date, nanoparticles have been exsolved from perovskite oxide surfaces using nonstoichiometric processes. However, the density of the space-separated nanoparticles on the oxide surfaces is still low. And less attention is paid toward the changes that happen to the host during the nanoparticle exsolution process. In this work, we demonstrated in situ exsolution of ultrafine nanoparticles (∼5 nm) of either Co3O4 or Ca(OH)2 via judicious control of nonstoichiometry in a misfit Ca3Co4O9 (CCO). The nanoparticle density over the CCO surface reached as high as 8500/µm2, which is significantly higher than previously reported values. High-resolution electron microscopy studies reveal the formation mechanism of Co3O4 nanoparticles over CCO, and the formation takes palace via the formation of wavy surfaces on the CCO. Defects caused by the nonstoichiometric synthesis created microstrain within the host CCO, resulting in making the new density of states near the Fermi energy. Further, the exsolution process turned the inert host (CCO) into electrocatalytically active toward water splitting. The nonstoichiometric samples obtained by shorter annealing times showed high electrocatalytic behavior for the hydrogen evolution (HER) and oxygen evolution (OER) reactions. The catalytic activity is further enhanced (reaching overpotential of 320 mV and 410 mV for HER and OER respectively, for a current density of 10 mA/cm2) by removing the surface nanoparticles. The observation indicates that the active sites that are produced during the nonstoichiometric synthesis also present in the bulk of the CCO (host). We believe that similar nonstoichiometric synthesis can be applied to a wide variety of tricomponent systems, and they could endow the hosts with novel properties for applications such as catalysis and thermoelectrics.

Hierarchically Engineered Nanocarbon Florets as Bifunctional Electrode Materials for Adsorptive and Intercalative Energy Storage.

Three-dimensional dendritic nanostructured carbon florets (NCFs) with tailored porosity are demonstrated as electrochemically versatile electrodes for both adsorptive and intercalative energy storage pathways. Achieved through a single-step template-driven approach, the NCFs exhibit turbostratic graphitic lamellae in a floral assembly leading to high specific surface area and multi-modal pore distribution (920 m2/g). The synergism in structural and chemical frameworks, along with open-ended morphology, enables bifunctionality of hard carbon NCFs as symmetric adsorptive electrodes for supercapacitors (SCs) and intercalation anodes for hybrid potassium-ion capacitors (KICs). Flexible, all-solid-state SCs through facile integration of NCF with the ionic-liquid-imbibed porous polymeric matrix achieve high-energy density (20 W h/kg) and power density (32.7 kW/kg) without compromising on mechanical flexibility and cyclability (94% after 20k cycles). Furthermore, NCF as an anode in a full-cell hybrid KIC (activated carbon as cathode) delivers excellent electrochemical performance with maximum energy and power densities of 57 W h/kg and 12.5 kW/kg, respectively, when cycled in a potential window of 1.0-4.0 V. The exceptional bifunctional performance of NCF highlights the possibility of utilizing such engineered nanocarbons for high-performance energy storage devices.

Interwoven Carbon Nanotube Wires for High-Performing, Mechanically Robust, Washable, and Wearable Supercapacitors.

An energy storage system with large storage capacity, rapid power release, and simultaneous tolerance to harsh mechanical stresses is a major bottleneck for realizing self-sustaining, wearable electronics. Addressing this, we demonstrate carbon nanotube wire (CNT-wire) interwoven solid-state supercapacitive energy storage devices (sewcaps) exhibiting superior storage capacity (30 Wh/kg, compared to electrochemical capacitors at ∼10 Wh/kg) and 14-fold higher power density (3511 W/kg) compared to Li-ion batteries (∼250 W/kg). While the high specific surface area and electrical conductivity of CNT-wires and high ionic conductivity of the electrolyte enable high energy density, the device design enables the combination of planar and radial diffusive pathways for ultralow interface resistance (∼0.2 mΩ/sewcap) and rapid charging-discharging ability (τ = 1.16 ms). Thus, this versatile approach of interweaving to form functional devices provides tunable power delivery across six orders of magnitude (2 µW to 2 W) through reconfiguration of the interweaving pattern and density. Importantly, such textile-integrated sewcaps exhibit unaltered performance (>95% retention across 4000 charge-discharge cycles) under extreme mechanical punishments such as repeated laundering, flexing (∼68°), rolling (360°), and crushing (∼21.8 kPa), implying direct interfacing with wearable platforms.

The mechanistic role of a support-catalyst interface in electrocatalytic water reduction by Co3O4 supported nanocarbon florets.

Comprehending the mechanistic involvement of a support-catalyst interface is critical for effective design of industrially relevant electrocatalytic processes such as the alkaline hydrogen evolution reaction (alHER). The understanding of the kinetically sluggish alHER exhibited by both Pt and Pt-group-metal-free catalysts is primarily derived from indirect electrochemical parameters such as the Tafel slope. To address these issues, we establish the critical role of a nanocarbon floret (NCF) based electrochemical support in generating a key cobalt-oxohydroxo (OH-Co[double bond, length as m-dash]O) intermediate during the alHER through operando Raman spectro-electrochemistry. Specifically, interfacial nano-engineering of a newly designed carbon support (NCF) with a spinel Co3O4 nanocube catalyst is demonstrated to achieve a facile alHER (-0.46 V@10 mA cm-2). Such an efficient alHER is mainly attributed to the unique lamellar morphology with a high mesoporous surface area (936 m2 g-1) of the NCF which catalyses the rate-determining water dissociation step and facilitates rapid ion diffusion. The dissociated water drives the formation of the OH-Co[double bond, length as m-dash]O intermediate, spectroscopically captured for the first time through the emergence of a νOH-Co[double bond, length as m-dash]O Raman peak (1074 cm-1). The subsequent alHER proceeds through the Volmer-Heyrovsky route (119 mV dec-1) via the Td Co2+↔ Co3+↔ Co4+ oxidative pathway. Concomitant graphitization of the NCF through the disappearance of νsp3C-H (2946 cm-1) supports the co-operative dynamics at the Co3O4-NCF interface. Thus, the NCF positively contributes towards the lowering of the overpotential with a low charge-transfer resistance (Rct = 35.8 Ω) and high double layer capacitance (Cdl = 410 mF cm-2).

Correction: Carbon nanotube-copper exhibiting metal-like thermal conductivity and silicon-like thermal expansion for efficient cooling of electronics.

Correction for 'Carbon nanotube-copper exhibiting metal-like thermal conductivity and silicon-like thermal expansion for efficient cooling of electronics' by Chandramouli Subramaniam and Kenji Hata et al., Nanoscale, 2014, 6, 2669-2674.

Exceptional photoconductivity of poly(3-hexylthiophene) fibers through in situ encapsulation of molybdenum disulfide quantum dots.

Photo-responsive, electrically conductive nanostructures are highly desirable for wide-ranging applications in energy harvesting, nanophotonic and optoelectronic devices. To this end, we realize self-assembled, photoconductive hybrids of poly(3-hexylthiophene) (P3HT) micro- and nano-fibers integrated with MoS2 quantum dots (QDs). We present an innovative strategy to impregnate QDs within the walls of the P3HT fibers resulting in the emergence of the controllable photoconductivity of the QD-P3HT hybrid. The maximum photoconductivity (>80% higher than pristine P3HT) is observed at 360 nm and originates from a synergistic combination of (a) defect healing and quenching of surface trap states in QDs by P3HT and (b) efficient generation and transfer of photo-excited charges from P3HT to QDs. This mechanism is substantiated by a concomitant decrease in the excited-state lifetime of the QD-P3HT hybrid. Furthermore, a linear correlation between the enhancement in the emission of QDs and the emission quenching of P3HT supports the proposed mechanism of excited-state charge transfer. Finally, the hybrid of MoS2 nanosheets (NS) with P3HT fibers (NS-P3HT) does not exhibit any photo-conductivity and instead exhibits ground state charge transfer, underlying the critical role of quantum confinement effects operating in the QD-P3HT hybrid. Thus, we demonstrate a synergistic, self-assembled QD-P3HT hybrid exhibiting optically controllable electrical conductivity in the solid state as novel functional materials for optoelectronic applications.

Electrochemical, top-down nanostructured pseudocapacitive electrodes for enhanced specific capacitance and cycling efficiency.

Stabilization of the electroactive redox centers on ideally polarisable conductive electrodes is a critical challenge for realizing stable, high performing pseudocapacitive energy storage devices. Here, we report a top-down, electrochemical nanostructuring route based on voltammetric cycling to stabilize ß-MnO2 on a single walled carbon nanotube (CNT) scaffold from a MnMoO4 precursor. Such in situ nanostructuring results in controlled disintegration of an ∼8 µm almond like structure to form ∼29 nm ß-MnO2 resulting in a 59% increase in the specific surface area and a 31% increase in the porosity of the pseudocapacitive electrode. Consequently, the specific capacitance and areal capacitance increase by ∼75% and ∼40%, respectively. Such controlled, top-down nanostructuring is confirmed through binding energy changes to Mo 3d, C 1s, O 1s and Mn 2p respectively in XPS. Furthermore, Raman spectral mapping confirms the sequential nanostructuring initiating from the interface of CNTs with MnMoO4 and proceeding outwards. Thus, the process yields the final CNT/ß-MnO2 electrode that is electrically conductive, facilitates rapid charge transfer, and has increased capacitance and longer stability. Furthermore, the charge-transfer resistance and equivalent resistance are significantly lower compared to conventional activated carbon based electrodes.

Scalable Approach to Highly Efficient and Rapid Capacitive Deionization with CNT-Thread As Electrodes.

A scalable route to highly efficient purification of water through capacitive deionization (CDI) is reported using CNT-thread as electrodes. Electro-sorption capacity (qe) of 139 mg g-1 and average salt-adsorption rate (ASAR) of 2.78 mg g-1min-1 achieved here is the highest among all known electrode materials and nonmembrane techniques, indicating efficient and rapid deionization. Such exceptional performance is achieved with feedstock concentrations (≤1000 ppm) where conventional techniques such as reverse osmosis and electrodialysis prove ineffective. Further, both cations (Na+, K+, Mg2+, and Ca2+) and anions (Cl-, SO42- and NO3-) are removed with equally high efficiency (∼80%). Synergism between electrical conductivity (∼25 S cm-1), high specific surface area (∼900 m2 g-1), porosity (0.7 nm, 3 nm) and hydrophilicity (contact angle ∼25°) in CNT-thread electrode enable superior contact with water, rapid formation of extensive electrical double layer and consequently efficient deionization. The tunable capacitance of the device (0.4-120 mF) and its high specific capacitance (∼27.2 F g-1) enable exceptional performance across a wide range of saline concentrations (50-1000 ppm). Facile regeneration of the electrode and reusability of the device is achieved for several cycles. The device demonstrated can desalinate water as it trickles down its surface because of gravity, thereby eliminating the requirement of any water pumping system. Finally, its portable adaptability is demonstrated by operating the device with an AA battery.

Real-Time, Wearable, Biomechanical Movement Capture of Both Humans and Robots with Metal-Free Electrodes.

We demonstrate an all-carbon-based, flexible, conformal movement-capturing device capable of precisely monitoring biomechanical movements of both humans and robots. Mechanically robust, metal-free electrodes form a unique component of the device responsible for qualitatively and quantitatively transducing biomechanical movements without any signal artifacts. Importantly, the device withstands and operates in a wide dynamic range for both stretching (25% strain) and bending (140°) actions with minimal cycling hysteresis (2.0), high repeatability (>100 cycles), low creep, and humidity-independent rapid response (∼200 ms). Furthermore, the device qualitatively distinguishes movements such as bending of finger, knuckle, and wrist and also provides quantitative information on the extent of such movements. We establish that single-wall carbon nanotubes (CNTs) embedded in ultralow concentration (0.016 wt %) within an elastomeric matrix undergo three-dimensional conformational changes during biomechanical movements that are subsequently transduced as signals. In addition, such CNT-elastomer strips exhibit enhanced stretchability (>100%) and elasticity (∼77%) in comparison to those of pure elastomers, leading to a wider dynamic working range of the device. Furthermore, seamless integration of a versatile gesture tracker on ubiquitous platforms, such as human skin, kinesiologic tapes, gloves, and robotic arms, is achieved, thereby catering to applications ranging from healthcare monitoring and physiotherapy to robotics and wearable technologies.

Nano-scale, planar and multi-tiered current pathways from a carbon nanotube-copper composite with high conductivity, ampacity and stability.

New lithographically processable materials with high ampacity are in demand to meet the increasing requirement for high operational current density at high temperatures existing in current pathways within electronic devices. To meet this demand, we report an approach to fabricate a high ampacity (∼100 times higher than Cu) carbon nanotube-copper (CNT-Cu) composite into a variety of complex nano-scale, planar and multi-tiered current pathways. The approach involved the use of a two-stage electrodeposition of copper into a pre-patterned template of porous, thin CNT sheets acting as the electrode. The versatility of this approach enabled the realization of completely suspended multi-tier, dielectric-less 'air-gap' CNT-Cu circuits that could be electrically isolated from each other and are challenging to fabricate with pure Cu or any metal. Importantly, all such complex structures, ranging from 500 nm to 20 µm in width, exhibited ∼100-times higher ampacity than any known metal, with comparable electrical conductivity as Cu. In addition, CNT-Cu structures also exhibited a superior temperature stability compared to the ∼10-times wider Cu counterparts. We believe that the combination of our approach and the properties demonstrated here are vital achievements for the future development of efficient and powerful electrical devices.

Influence of matching solubility parameter of polymer matrix and CNT on electrical conductivity of CNT/rubber composite.

We report a general approach to fabricate elastomeric composites possessing high electrical conductivity for applications ranging from wireless charging interfaces to stretchable electronics. By using arbitrary nine kinds of rubbers as matrices, we experimentally demonstrate that the matching the solubility parameter of CNTs and the rubber matrix is important to achieve higher electrical conductivity in CNT/rubber composite, resulting in continuous conductive pathways leading to electrical conductivities as high as 15 S/cm with 10 vol% CNT in fluorinated rubber. Further, using thermodynamic considerations, we demonstrate an approach to mix CNTs to arbitrary rubber matrices regardless of solubility parameter of matrices by adding small amounts of fluorinated rubber as a polymeric-compatibilizer of CNTs. We thereby achieved electrical conductivities ranging from 1.2 to 13.8 S/cm (10 vol% CNTs) using nine varieties of rubber matrices differing in chemical structures and physical properties. Finally, we investigated the components of solubility parameter of CNT by using Hansen solubility parameters, these findings may useful for controlling solubility parameter of CNTs.