preparation-evaluation-hybrid-composites-chemical-fuel-multi-walled

Preparation and Evaluation of Hybrid Composites of Chemical Fuel and Multi-walled Carbon Nanotubes in the Study of Thermopower Waves

When a chemical fuel at a certain position in a hybrid composite of the fuel and a micro/nanostructured material is ignited, chemical combustion occurs ...

Theoretical calculations predict that by coupling an exothermic chemical reaction with a nanotube or nanowire possessing a high axial thermal conductivity, a self-propagating reactive wave can be driven along its length. Herein, such waves are realized using a 7-nm cyclotrimethylene trinitramine annular shell around a multiwalled carbon nanotube and are amplified by more than 10(4) times the bulk value, propagating faster than 2 m s(-1), with an effective thermal conductivity of 1.28+/-0.2 kW m(-1) K(-1) at 2,860 K. This wave produces a concomitant electrical pulse of disproportionately high specific power, as large as 7 kW kg(-1), which we identify as a thermopower wave. Thermally excited carriers flow in the direction of the propagating reaction with a specific power that scales inversely with system size. The reaction also evolves an anisotropic pressure wave of high total impulse per mass (300 N s kg(-1)). Such waves of high power density may find uses as unique energy sources.

Chemically driven carbon-nanotube-guided thermopower waves.

Biological ion channels are able to generate coherent and oscillatory signals from intrinsically noisy and stochastic components for ultrasensitive discrimination with the use of stochastic resonance, a concept not yet demonstrated in human-made analogs. We show that a single-walled carbon nanotube demonstrates oscillations in electroosmotic current through its interior at specific ranges of electric field that are the signatures of coherence resonance. Stochastic pore blocking is observed when individual cations partition into the nanotube obstructing an otherwise stable proton current. The observed oscillations occur because of coupling between pore blocking and a proton-diffusion limitation at the pore mouth. The result illustrates how simple ionic transport can generate coherent waveforms within an inherently noisy environment and points to new types of nanoreactors, sensors, and nanofluidic channels based on this platform.

Coherence resonance in a single-walled carbon nanotube ion channel.

There is significant interest in combining carbon nanotubes with semiconducting polymers for photovoltaic applications because of potential advantages from smaller exciton transport lengths and enhanced charge separation. However, to date, bulk heterojunction (BHJ) devices have demonstrated relatively poor efficiencies, and little is understood about the polymer/nanotube junction. To investigate this interface, we fabricate a planar nano-heterojunction comprising well-isolated millimeter-long single-walled carbon nanotubes underneath a poly(3-hexylthiophene) (P3HT) layer. The resulting junctions display photovoltaic efficiencies per nanotube ranging from 3% to 3.82%, which exceed those of polymer/nanotube BHJs by a factor of 50-100. The increase is attributed to the absence of aggregate formation in this planar device geometry. It is shown that the polymer/nanotube interface itself is responsible for exciton dissociation. Typical open-circuit voltages are near 0.5 V with fill factors of 0.25-0.3, which are largely invariant with the number of nanotubes per device and P3HT thickness. A maximum efficiency is obtained for a 60 nm-thick P3HT layer, which is predicted by a Monte Carlo simulation that takes into account exciton generation, transport, recombination, and dissociation. This platform is promising for further understanding the potential role of polymer/nanotube interfaces for photovoltaic applications.

Evidence for high-efficiency exciton dissociation at polymer/single-walled carbon nanotube interfaces in planar nano-heterojunction photovoltaics.

The ability to actively manipulate and transport single molecules in solution has the potential to revolutionize chemical synthesis and catalysis. In previous work, we developed a nanopore platform using the interior of a single-walled carbon nanotube (diameter = 1.5 nm) for the Coulter detection of single cations of Li(+), K(+), and Na(+). We demonstrate that as a result of their fabrication, such systems have electrostatic barriers present at their ends that are generally asymmetric, allowing for the trapping of ions. We show that above this threshold bias, traversing the nanopore end is not rate-limiting and that the pore-blocking behavior of two parallel nanotubes follows an idealized Markov process with the electrical potential. Such nanopores may allow for high-throughput linear processing of molecules as new catalysts and separation devices.

Dynamics of simultaneous, single ion transport through two single-walled carbon nanotubes: observation of a three-state system.

The nonlinear coupling between exothermic chemical reactions and a nanowire or nanotube with large axial heat conduction results in a self-propagating thermal wave guided along the nanoconduit. The resulting reaction wave induces a concomitant thermopower wave of high power density (>7 kW/kg), resulting in an electrical current along the same direction. We develop the theory of such waves and analyze them experimentally, showing that for certain values of the chemical reaction kinetics and thermal parameters, oscillating wavefront velocities are possible. We demonstrate such oscillations experimentally using a cyclotrimethylene-trinitramine/multiwalled carbon nanotube system, which produces frequencies in the range of 400 to 5000 Hz. The propagation velocity oscillations and the frequency dispersion are well-described by Fourier's law with an Arrhenius source term accounting for reaction and a linear heat exchange with the nanotube scaffold. The frequencies are in agreement with oscillations in the voltage generated by the reaction. These thermopower oscillations may enable new types of nanoscale power and signal processing sources.

Wavefront velocity oscillations of carbon-nanotube-guided thermopower waves: nanoscale alternating current sources.

Self-propagating exothermic chemical reactions can generate electrical pulses when guided along a conductive conduit such as a carbon nanotube. However, these thermopower waves are not described by an existing theory to explain the origin of power generation or why its magnitude exceeds the predictions of the Seebeck effect. In this work, we present a quantitative theory that describes the electrical dynamics of thermopower waves, showing that they produce an excess thermopower additive to the Seebeck prediction. Using synchronized, high-speed thermal, voltage, and wave velocity measurements, we link the additional power to the chemical potential gradient created by chemical reaction (up to 100 mV for picramide and sodium azide on carbon nanotubes). This theory accounts for the waves' unipolar voltage, their ability to propagate on good thermal conductors, and their high power, which is up to 120% larger than conventional thermopower from a fiber of all-semiconducting SWNTs. These results underscore the potential to exceed conventional figures of merit for thermoelectricity and allow us to bound the maximum power and efficiency attainable for such systems.

Excess thermopower and the theory of thermopower waves.

Nanopores that approach molecular dimensions demonstrate exotic transport behaviour and are theoretically predicted to display discontinuities in the diameter dependence of interior ion transport because of structuring of the internal fluid. No experimental study has been able to probe this diameter dependence in the 0.5-2 nm diameter regime. Here we observe a surprising fivefold enhancement of stochastic ion transport rates for single-walled carbon nanotube centered at a diameter of approximately 1.6 nm. An electrochemical transport model informed from literature simulations is used to understand the phenomenon. We also observe rates that scale with cation type as Li(+)>K(+)>Cs(+)>Na(+) and pore blocking extent as K(+)>Cs(+)>Na(+)>Li(+) potentially reflecting changes in hydration shell size. Across several ion types, the pore-blocking current and inverse dwell time are shown to scale linearly at low electric field. This work opens up new avenues in the study of transport effects at the nanoscale.

Diameter-dependent ion transport through the interior of isolated single-walled carbon nanotubes.

Thermopower wave is a new concept of energy conversion from chemical to thermal to electrical energy, produced from the chemical reaction in well-designed hybrid structures between nanomaterials and combustible fuels. The enhancement and optimization of energy generation is essential to make it useful for future applications. In this study, we demonstrate that simple solution-based synthesized zinc oxide (ZnO) nanostructures, such as nanorods and nanoparticles are capable of generating high output voltage from thermopower waves. In particular, an astonishing improvement in the output voltage (up to 3 V; average 2.3 V) was achieved in a ZnO nanorods-based composite film with a solid fuel (collodion, 5% nitrocellulose), which generated an exothermic chemical reaction. Detailed analyses of thermopower waves in ZnO nanorods- and cube-like nanoparticles-based hybrid composites have been reported in which nanostructures, output voltage profile, wave propagation velocities, and surface temperature have been characterized. The average combustion velocities for a ZnO nanorods/fuel and a ZnO cube-like nanoparticles/fuel composites were 40.3 and 30.0 mm/s, while the average output voltages for these composites were 2.3 and 1.73 V. The high output voltage was attributed to the amplified temperature in intermixed composite of ZnO nanostructures and fuel due to the confined diffusive heat transfer in nanostructures. Moreover, the extended interfacial areas between ZnO nanorods and fuel induced large amplification in the dynamic change of the chemical potential, and it resulted in the enhanced output voltage. The differences of reaction velocity and the output voltage between ZnO nanorods- and ZnO cube-like nanoparticles-based composites were attributed to variations in electron mobility and grain boundary, as well as thermal conductivities of ZnO nanorods and particles. Understanding this astonishing increase and the variation of the output voltage and reaction velocity, precise ZnO nanostructures, will help in formulating specific strategies for obtaining enhanced energy generation from thermopower waves.

Advanced Thermopower Wave in Novel ZnO Nanostructures/Fuel Composite.

Thermopower waves are a recently developed energy conversion concept utilizing dynamic temperature and chemical potential gradients to harvest electrical energy while the combustion wave propagates along the hybrid layers of nanomaterials and chemical fuels. The intrinsic properties of the core nanomaterials and chemical fuels in the hybrid composites can broadly affect the energy generation, as well as the combustion process, of thermopower waves. So far, most research has focused on the application of new core nanomaterials to enhance energy generation. In this study, we demonstrate that the alignment of core nanomaterials can significantly influence a number of aspects of the thermopower waves, while the nanomaterials involved are identical carbon nanotubes (CNTs). Diversely structured, large-area CNT/fuel composites of one-dimensional aligned CNT arrays (1D CNT arrays), randomly oriented CNT films (2D CNT films), and randomly aggregated bulk CNT clusters (3D CNT clusters) were fabricated to evaluate the energy generation, as well as the propagation of the thermal wave, from thermopower waves. The more the core nanostructures were aligned, the less inversion of temperature gradients and the less cross-propagation of multiple thermopower waves occurred. These characteristics of the aligned structures prevented the cancellation of charge carrier movements among the core nanomaterials and produced the relative enhancement of the energy generation and the specific power with a single-polarity voltage signal. Understanding this effect of structure on energy generation from thermopower waves can help in the design of optimized hybrid composites of nanomaterials and fuels, especially designs based on the internal alignment of the materials. More generally, we believe that this work provides clues to the process of chemical to thermal to electrical energy conversion inside/outside hybrid nanostructured materials.

Investigation of the effect of the structure of large-area carbon nanotube/fuel composites on energy generation from thermopower waves.

Thermopower waves, which occur during combustion within hybrid structures formed from nanomaterials and chemical fuels, result in a self-propagating thermal reaction and concomitantly generate electrical energy from the acceleration of charge carriers along the nanostructures. The hybrid structures for thermopower waves are composed of two primary components: the core thermoelectric material and the combustible fuel. So far, most studies have focused on investigating various nanomaterials for improving energy generation. Herein, we report that the composition of the chemical fuel used has a significant effect on the power generated by thermopower waves. Hybrid nanostructures consisting of mixtures of picric acid and picramide with sodium azide were synthesized and used to generate thermopower waves. A maximum voltage of ∼2 V and an average peak specific power as high as 15 kW kg(-1) were obtained using the picric acid/sodium azide/multiwalled carbon nanotubes (MWCNTs) array composite. The average reaction velocity and the output voltage in the case of the picric acid/sodium azide were 25 cm s(-1) and 157 mV, while they were 2 cm s(-1) and 3 mV, in the case of the picramide/sodium azide. These marked differences are attributable to the chemical and structural differences of the mixtures. Mixing picric acid and sodium azide in deionized water resulted in the formation of 2,4,6-trinitro sodium phenoxide and hydrogen azide (H-N3), owing to the exchange of H(+) and Na(+) ions, as well as the formation of fiber-like structures, because of benzene π stacking. The negative enthalpy of formation of the new compounds and the fiber-like structures accelerate the reaction and increase the output voltage. Elucidating the effects of the composition of the chemical fuel used in the hybrid nanostructures will allow for the control of the combustion process and help optimize the energy generated from thermopower waves, furthering the development of thermopower waves as an energy source.

Article	Year
Chemically driven carbon-nanotube-guided thermopower waves. Nature materials\| PubMed ID: 20208525	2010
Coherence resonance in a single-walled carbon nanotube ion channel. Science (New York, N.Y.)\| PubMed ID: 20829480	2010
Evidence for high-efficiency exciton dissociation at polymer/single-walled carbon nanotube interfaces in planar nano-heterojunction photovoltaics. ACS nano\| PubMed ID: 20886891	2010
Dynamics of simultaneous, single ion transport through two single-walled carbon nanotubes: observation of a three-state system. Journal of the American Chemical Society\| PubMed ID: 21166470	2011
Wavefront velocity oscillations of carbon-nanotube-guided thermopower waves: nanoscale alternating current sources. ACS nano\| PubMed ID: 21182252	2011
Excess thermopower and the theory of thermopower waves. ACS nano\| PubMed ID: 23889080	2013
Diameter-dependent ion transport through the interior of isolated single-walled carbon nanotubes. Nature communications\| PubMed ID: 24025921	2013
Advanced Thermopower Wave in Novel ZnO Nanostructures/Fuel Composite. ACS applied materials & interfaces\| PubMed ID: 25133980	2014
Investigation of the effect of the structure of large-area carbon nanotube/fuel composites on energy generation from thermopower waves. Nanoscale research letters\| PubMed ID: 25285059	2014
Effects of chemical fuel composition on energy generation from thermopower waves. Nanotechnology\| PubMed ID: 25319506	2014

Wonjoon Choi

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