Solvent-induced electrochemistry at an electrically asymmetric carbon Janus particle.

Chemical doping through heteroatom substitution is often used to control the Fermi level of semiconductor materials. Doping also occurs when surface adsorbed molecules modify the Fermi level of low dimensional materials such as carbon nanotubes. A gradient in dopant concentration, and hence the chemical potential, across such a material generates usable electrical current. This opens up the possibility of creating asymmetric catalytic particles capable of generating voltage from a surrounding solvent that imposes such a gradient, enabling electrochemical transformations. In this work, we report that symmetry-broken carbon particles comprised of high surface area single-walled carbon nanotube networks can effectively convert exothermic solvent adsorption into usable electrical potential, turning over electrochemical redox processes in situ with no external power supply. The results from ferrocene oxidation and the selective electro-oxidation of alcohols underscore the potential of solvent powered electrocatalytic particles to extend electrochemical transformation to various environments.

Colloidal nanoelectronic state machines based on 2D materials for aerosolizable electronics.

A previously unexplored property of two-dimensional electronic materials is their ability to graft electronic functionality onto colloidal particles to access local hydrodynamics in fluids to impart mobility and enter spaces inaccessible to larger electronic systems. Here, we demonstrate the design and fabrication of fully autonomous state machines built onto SU-8 particles powered by a two-dimensional material-based photodiode. The on-board circuit connects a chemiresistor circuit element and a memristor element, enabling the detection and storage of information after aerosolization, hydrodynamic propulsion to targets over 0.6 m away, and large-area surface sensing of triethylamine, ammonia and aerosolized soot in inaccessible locations. An incorporated retroreflector design allows for facile position location using laser-scanning optical detection. Such state machines may find widespread application as probes in confined environments, such as the human digestive tract, oil and gas conduits, chemical and biosynthetic reactors, and autonomous environmental sensors.

Ultra-high thermal effusivity materials for resonant ambient thermal energy harvesting.

Materials science has made progress in maximizing or minimizing the thermal conductivity of materials; however, the thermal effusivity-related to the product of conductivity and capacity-has received limited attention, despite its importance in the coupling of thermal energy to the environment. Herein, we design materials that maximize the thermal effusivity by impregnating copper and nickel foams with conformal, chemical-vapor-deposited graphene and octadecane as a phase change material. These materials are ideal for ambient energy harvesting in the form of what we call thermal resonators to generate persistent electrical power from thermal fluctuations over large ranges of frequencies. Theory and experiment demonstrate that the harvestable power for these devices is proportional to the thermal effusivity of the dominant thermal mass. To illustrate, we measure persistent energy harvesting from diurnal frequencies, extracting as high as 350 mV and 1.3 mW from approximately 10 °C diurnal temperature differences.

Noble-gas-infused neoprene closed-cell foams achieving ultra-low thermal conductivity fabrics.

Closed-cell foams are widely applied as insulation and essential for the thermal management of protective garments for extreme environments. In this work, we develop and demonstrate a strategy for drastically reducing the thermal conductivity of a flexible, closed-cell polychloroprene foam to 0.031 ± 0.002 W m-1 K-1, approaching values of an air gap (0.027 W m-1 K-1) for an extended period of time (>10 hours), within a material capable of textile processing. Ultra-insulating neoprene materials are synthesized using high-pressure processing at 243 kPa in a high-molecular-weight gas environment, such as Ar, Kr, or Xe. A Fickian diffusion model describes both the mass infusion and thermal conductivity reduction of the foam as a function of processing time, predicting a 24-72 hour required exposure time for full charging of a 6 mm thick 5 cm diameter neoprene sample. These results enable waterproof textile insulation that approximates a wearable air gap. We demonstrate a wetsuit made of ultra-low thermally conductive neoprene capable of potentially extending dive times to 2-3 hours in water below 10 °C, compared with <1 hour for the state-of-the-art. This work introduces the prospect of effectively wearing a flexible air gap for thermal protection in harsh environments.

Observation of the Marcus Inverted Region of Electron Transfer from Asymmetric Chemical Doping of Pristine (n,m) Single-Walled Carbon Nanotubes.

The concept of electrical energy generation based on asymmetric chemical doping of single-walled carbon nanotube (SWNT) papers is presented. We explore 27 small, organic, electron-acceptor molecules that are shown to tune the output open-circuit voltage (VOC) across three types of pristine SWNT papers with varying (n,m) chirality distributions. A considerable enhancement in the observed VOC, from 80 to 440 mV, is observed for SWNT/molecule acceptor pairs that have molecular volume below 120 Å3 and lowest unoccupied molecular orbital (LUMO) energies centered around -0.8 eV. The electron transfer (ET) rate constants driving the VOC generation are shown to vary with the chirality-associated Marcus theory, suggesting that the energy gaps between SWNT and the LUMO of acceptor molecules dictate the ET process. When the ET rate constants and the maximum VOC are plotted versus the LUMO energy of the acceptor organic molecule, volcano-shaped dependencies, characteristic of the Marcus inverted region, are apparent for three distinct sources of SWNT papers with modes in diameter distributions of 0.95, 0.83, and 0.75 nm. This observation, where the ET driving force exceeds reorganization energies, allows for an estimation of the outer-sphere reorganization energies with values as low as 100 meV for the (8,7) SWNT, consistent with a proposed image-charge modified Born energy model. These results expand the fundamental understanding of ET transfer processes in SWNT and allow for an accurate calculation of energy generation through asymmetric doping for device applications.

Microscale solid-state thermal diodes enabling ambient temperature thermal circuits for energy applications.

Thermal diodes, or devices that transport thermal energy asymmetrically, analogous to electrical diodes, hold promise for thermal energy harvesting and conservation, as well as for phononics or information processing. The junction of a phase change material and phase invariant material can form a thermal diode; however, there are limited constituent materials available for a given target temperature, particularly near ambient. In this work, we demonstrate that a micro and nanoporous polystyrene foam can house a paraffin-based phase change material, fused to PMMA, to produce mechanically robust, solid-state thermal diodes capable of ambient operation with Young's moduli larger than 11.5 MPa and 55.2 MPa above and below the melting transition point, respectively. Moreover, the composites show significant changes in thermal conductivity above and below the melting point of the constituent paraffin and rectification that is well-described by our previous theory and the Maxwell-Eucken model. Maximum thermal rectifications range from 1.18 to 1.34. We show that such devices perform reliably enough to operate in thermal diode bridges, dynamic thermal circuits capable of transforming oscillating temperature inputs into single polarity temperature differences - analogous to an electrical diode bridge with widespread implications for transient thermal energy harvesting and conservation. Overall, our approach yields mechanically robust, solid-state thermal diodes capable of engineering design from a mathematical model of phase change and thermal transport, with implications for energy harvesting.

Electrical Energy Generation via Reversible Chemical Doping on Carbon Nanotube Fibers.

Chemically modified carbon nanotube fibers enable unique power sources driven entirely by a chemical potential gradient. Electrical current (11.9 µA mg-1 ) and potential (525 mV) are reversibly produced by localized acetonitrile doping under ambient conditions. An inverse length-scaling of the maximum power as L-1.03 that creates specific powers as large as 30.0 kW kg-1 highlights the potential for microscale energy generation.