Fuel-Driven Redox Reactions in Electrolyte-Free Polymer Actuators for Soft Robotics.

Polymers that undergo shape changes in response to external stimuli can serve as actuators and offer significant potential in a variety of technologies, including biomimetic artificial muscles and soft robotics. Current polymer artificial muscles possess major challenges for various applications as they often require extreme and non-practical actuation conditions. Thus, exploring actuators with new or underutilized stimuli may broaden the application of polymer-based artificial muscles. Here, we introduce an all-solid fuel-powered actuator that contracts and expands when exposed to H2 and O2 via redox reactions. This actuator demonstrates a fully reversible actuation magnitude of up to 3.8% and achieves a work capacity of 120 J/kg. Unlike traditional chemical actuators, our actuator eliminates the need for electrolytes, electrodes, and the application of external voltage. Moreover, it offers athermal actuation by avoiding the drawbacks of thermal actuators. Remarkably, the actuator maintains its actuated position under load when not stimulated, without consuming energy (i.e., catch state). These fuel-powered fiber actuators were embedded in a soft humanoid hand to demonstrate finger-bending motions. In terms of two main actuation metrics, stress-free contraction strain and blocking stress, the presented artificial muscle outperforms reported polymer redox actuators. The fuel-powered actuator developed in this work creates new avenues for the application of redox polymers in soft robotics and artificial muscles.

Lattice Strain and Surface Activity of Ternary Nanoalloys under the Propane Oxidation Condition.

The ability to harness the catalytic oxidation of hydrocarbons is critical for both clean energy production and air pollutant elimination, which requires a detailed understanding of the dynamic role of the nanophase structure and surface reactivity under the reaction conditions. We report here findings of an in situ/operando study of such details of a ternary nanoalloy under the propane oxidation condition using high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The catalysts are derived by alloying Pt with different combinations of second (Pd) and third (Ni) transition metals, showing a strong dependence of the catalytic activity on the Ni content. The evolution of the phase structure of the nanoalloy is characterized by HE-XRD/PDF probing of the lattice strain, whereas the surface activity is monitored by DRIFTS detection of the surface intermediate formation during the oxidation of propane by oxygen. The results reveal the dominance of the surface intermediate species featuring a lower degree of oxygenation upon the first C-C bond cleavage on the lower-Ni-content nanoalloy and a higher degree of oxygenation upon the second C-C bond cleavage on the higher-Ni-content nanoalloy. The face-centered-cubic-type phase structures of the nanoalloys under the oxidation condition are shown to exhibit Ni-content-dependent changes of lattice strains, featuring the strongest strain with little variation for the higher-Ni-content nanoalloy, in contrast to the weaker strains with oscillatory variation for the lower-Ni-content nanoalloys. This process is also accompanied by oxygenation of the metal components in the nanoalloy, showing a higher degree of oxygenation for the higher-Ni-content nanoalloy. These subtle differences in phase structure and surface activity changes correlate with the Ni-composition-dependent catalytic activity of the nanoalloys, which sheds a fresh light on the correlation between the dynamic change of atomic strains and the surface reactivity and has significant implications for the design of oxidation catalysts with enhanced activities.

Vapor-fed bio-hybrid fuel cell.

BACKGROUND: Concentration and purification of ethanol and other biofuels from fermentations are energy-intensive processes, with amplified costs at smaller scales. To circumvent the need for these processes, and to potentially reduce transportation costs as well, we have previously investigated bio-hybrid fuel cells (FCs), in which a fermentation and FC are closely coupled. However, long-term operation requires strictly preventing the fermentation and FC from harming each other. We introduce here the concept of the vapor-fed bio-hybrid FC as a means of continuously extracting power from ongoing fermentations at ambient conditions. By bubbling a carrier gas (N2) through a yeast fermentation and then through a direct ethanol FC, we protect the FC anode from the catalyst poisons in the fermentation (which are non-volatile), and also protect the yeast from harmful FC products (notably acetic acid) and from build-up of ethanol. RESULTS: Since vapor-fed direct ethanol FCs at ambient conditions have never been systematically characterized (in contrast to vapor-fed direct methanol FCs), we first assess the effects on output power and conversion efficiency of ethanol concentration, vapor flow rate, and FC voltage. The results fit a continuous stirred-tank reactor model. Over a wide range of ethanol partial pressures (2-8 mmHg), power densities are comparable to those for liquid-fed direct ethanol FCs at the same temperature, with power densities >2 mW/cm2 obtained. We then demonstrate the continuous operation of a vapor-fed bio-hybrid FC with fermentation for 5 months, with no indication of performance degradation due to poisoning (of either the FC or the fermentation). It is further shown that the system is stable, recovering quickly from disturbances or from interruptions in maintenance. CONCLUSIONS: The vapor-fed bio-hybrid FC enables extraction of power from dilute bio-ethanol streams without costly concentration and purification steps. The concept should be scalable to both large and small operations and should be generalizable to other biofuels and waste-to-energy systems.

Aspergillus oryzae-Saccharomyces cerevisiae Consortium Allows Bio-Hybrid Fuel Cell to Run on Complex Carbohydrates.

Consortia of Aspergillus oryzae and Saccharomyces cerevisiae are examined for their abilities to turn complex carbohydrates into ethanol. To understand the interactions between microorganisms in consortia, Fourier-transform infrared spectroscopy is used to follow the concentrations of various metabolites such as sugars (e.g., glucose, maltose), longer chain carbohydrates, and ethanol to optimize consortia conditions for the production of ethanol. It is shown that with proper design A. oryzae can digest food waste simulants into soluble sugars that S. cerevisiae can ferment into ethanol. Depending on the substrate and conditions used, concentrations of 13% ethanol were achieved in 10 days. It is further shown that a direct alcohol fuel cell (FC) can be coupled with these A. oryzae-enabled S. cerevisiae fermentations using a reverse osmosis membrane. This "bio-hybrid FC" continually extracted ethanol from an ongoing consortium, enhancing ethanol production and allowing the bio-hybrid FC to run for at least one week. Obtained bio-hybrid FC currents were comparable to those from pure ethanol-water mixtures, using the same FC. The A. oryzae-S. cerevisiae consortium, coupled to a bio-hybrid FC, converted food waste simulants into electricity without any pre- or post-processing.

Simple, fast, and accurate methodology for quantitative analysis using Fourier transform infrared spectroscopy, with bio-hybrid fuel cell examples.

The standard methodologies for quantitative analysis (QA) of mixtures using Fourier transform infrared (FTIR) instruments have evolved until they are now more complicated than necessary for many users' purposes. We present a simpler methodology, suitable for widespread adoption of FTIR QA as a standard laboratory technique across disciplines by occasional users.•Algorithm is straightforward and intuitive, yet it is also fast, accurate, and robust.•Relies on component spectra, minimization of errors, and local adaptive mesh refinement.•Tested successfully on real mixtures of up to nine components. We show that our methodology is robust to challenging experimental conditions such as similar substances, component percentages differing by three orders of magnitude, and imperfect (noisy) spectra. As examples, we analyze biological, chemical, and physical aspects of bio-hybrid fuel cells.

Excited-state absorption of a bipyridyl platinum(II) complex with alkynyl-benzothiazolylfluorene units.

The singlet excited-state lifetime of a bipyridyl platinum(II) complex containing two alkynyl-benzothiazolylfluorene units was determined to be 145+/-105 ps by fitting femtosecond transient difference absorption data, and the triplet quantum yield was measured to be 0.14. A ground-state absorption cross section of 6.1 x 10(-19) cm(2) at 532 nm was deduced from UV-visible absorption data. Excited-state absorption cross sections of (6.7+/-0.1) x 10(-17) cm(2) (singlet) and (4.6+/-0.1) x 10(-16) cm(2) (triplet) were obtained by using a five-level dynamic model to fit open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies. For this complex, the ratio of the triplet excited-state absorption cross section to the ground-state absorption cross section--long used as a figure of merit for reverse saturable absorbers--thus stands at 754, to our knowledge the largest ever reported at 532 nm wavelength.

Photophysical properties of C60 colloids suspended in water with Triton X-100 surfactant: excited-state properties with femtosecond resolution.

We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.

Multimode interference devices with input-output ports on the sides.

Multimode interference (MMI) devices are useful for power splitting and for the separation or combination of wavelengths or polarizations, usually in integrated optics. Input-output guides connect to the MMI region by ports. In all previously reported MMI devices, the input and output guides connect only to the ends of the MMI region; i.e., they are end ported. What is believed to be a novel arrangement of the input-output ports on MMI devices is described. By placing input-output ports either partially or entirely on the sides of the MMI region (i.e., side porting), a variety of benefits are achieved and a variety of new devices can be made.

Slotted multimode-interference devices.

We describe a novel modification of multimode-interference devices that has broad applicability. The modification involves introducing a slot (or slots), of a specific width and effective refractive index and at a specific position, that runs the longitudinal length of the multimode-interference region. Introducing N slots reduces the self-image length by a factor of N + 1. Varying the effective refractive index or width of the slot(s) creates a switch. The slot modification can be accomplished in a variety of ways, actually increases bandwidth, and has good error tolerances.

Preoptimization improvements to subwavelength diffractive lenses.

We present preoptimization strategies for improving the design of diffractive lenses in the electromagnetic domain, with few or no electromagnetic analyses. We find that improvements can be substantial, in some cases even to the point that extensive electromagnetic optimization gives only marginal additional improvement.