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Broadband absorbers are essential components of many light detection, energy harvesting, and camouflage schemes. Current designs are either bulky or use planar films that cause problems in cracking and delamination during flexing or heating. In addition, transferring planar materials to flexible, thin, or low-cost substrates poses a significant challenge. On the other hand, particle-based materials are highly flexible and can be transferred and assembled onto a more desirable substrate but have not shown high performance as an absorber in a standalone system. Here, we introduce a class of particle absorbers called transferable hyperbolic metamaterial particles (THMMP) that display selective, omnidirectional, tunable, broadband absorption when closely packed. This is demonstrated with vertically aligned hyperbolic nanotube (HNT) arrays composed of alternating layers of aluminum-doped zinc oxide and zinc oxide. The broadband absorption measures >87% from 1,200 nm to over 2,200 nm with a maximum absorption of 98.1% at 1,550 nm and remains large for high angles. Furthermore, we show the advantages of particle-based absorbers by transferring the HNTs to a polymer substrate that shows excellent mechanical flexibility and visible transparency while maintaining near-perfect absorption in the telecommunications region. In addition, other material systems and geometries are proposed for a wider range of applications.
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Aluminum-doped zinc oxide (AZO) is a tunable low-loss plasmonic material capable of supporting dopant concentrations high enough to operate at telecommunication wavelengths. Due to its ultrahigh conformality and compatibility with semiconductor processing, atomic layer deposition (ALD) is a powerful tool for many plasmonic applications. However, despite many attempts, high-quality AZO with a plasma frequency below 1550 nm has not yet been realized by ALD. Here a simple procedure is devised to tune the optical constants of AZO and enable plasmonic activity at 1550 nm with low loss. The highly conformal nature of ALD is also exploited to coat silicon nanopillars to create localized surface plasmon resonances that are tunable by adjusting the aluminum concentration, thermal conditions, and the use of a ZnO buffer layer. The high-quality AZO is then used to make a layered AZO/ZnO structure that displays negative refraction in the telecommunication wavelength region due to hyperbolic dispersion. Finally, a novel synthetic scheme is demonstrated to create AZO embedded nanowires in ZnO, which also exhibits hyperbolic dispersion.
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We report an ultrathin NiOx catalyzed Si np(+) junction photoanode for a stable and efficient solar driven oxygen evolution reaction (OER) in water. A stable semi-transparent ITO/Au/ITO hole conducting oxide layer, sandwiched between the OER catalyst and the Si photoanode, is used to protect the Si from corrosion in an alkaline working environment, enhance the hole transportation, and provide a pre-activation contact to the NiOx catalyst. The NiOx catalyzed Si photoanode generates a photocurrent of 1.98 mA cm(-2) at the equilibrium water oxidation potential (EOER = 0.415 V vs. NHE in 1 M NaOH solution). A thermodynamic solar-to-oxygen conversion efficiency (SOCE) of 0.07% under 0.51-sun illumination is observed. The successful development of a low cost, highly efficient, and stable photoelectrochemical electrode based on earth abundant elements is essential for the realization of a large-scale practical solar fuel conversion.
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Dioxygen (O(2)) and other gas molecules have a fundamental role in a variety of enzymatic reactions. However, it is only poorly understood which O(2) uptake mechanism enzymes employ to promote efficient catalysis and how general this is. We investigated O(2) diffusion pathways into monooxygenase and oxidase flavoenzymes, using an integrated computational and experimental approach. Enhanced-statistics molecular dynamics simulations reveal spontaneous protein-guided O(2) diffusion from the bulk solvent to preorganized protein cavities. The predicted protein-guided diffusion paths and the importance of key cavity residues for oxygen diffusion were verified by combining site-directed mutagenesis, rapid kinetics experiments, and high-resolution X-ray structures. This study indicates that monooxygenase and oxidase flavoenzymes employ multiple funnel-shaped diffusion pathways to absorb O(2) from the solvent and direct it to the reacting C4a atom of the flavin cofactor. The difference in O(2) reactivity among dehydrogenases, monooxygenases, and oxidases ultimately resides in the fine modulation of the local environment embedding the reactive locus of the flavin.
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Flavoproteínas/química , Oxidorreductasas/química , Oxígeno/química , Oxidorreductasas de Alcohol/química , Oxidorreductasas de Alcohol/genética , Oxidorreductasas de Alcohol/metabolismo , Catálisis , Dominio Catalítico/genética , Simulación por Computador , Cristalografía por Rayos X , Difusión , Flavinas/química , Flavinas/metabolismo , Flavoproteínas/genética , Flavoproteínas/metabolismo , Modelos Moleculares , Mutagénesis Sitio-Dirigida , Oxidorreductasas/genética , Oxidorreductasas/metabolismo , Oxígeno/metabolismo , Unión Proteica , Estructura Terciaria de Proteína , Streptomyces coelicolor/enzimologíaRESUMEN
Central to advancing our understanding of neural circuits is developing minimally invasive, multi-modal interfaces capable of simultaneously recording and modulating neural activity. Recent devices have focused on matching the mechanical compliance of tissue to reduce inflammatory responses. However, reductions in the size of multi-modal interfaces are needed to further improve biocompatibility and long-term recording capabilities. Here a multi-modal coaxial microprobe design with a minimally invasive footprint (8-14 µm diameter over millimeter lengths) that enables efficient electrical and optical interrogation of neural networks is presented. In the brain, the probes allowed robust electrical measurement and optogenetic stimulation. Scalable fabrication strategies can be used with various electrical and optical materials, making the probes highly customizable to experimental requirements, including length, diameter, and mechanical properties. Given their negligible inflammatory response, these probes promise to enable a new generation of readily tunable multi-modal devices for long-term, minimally invasive interfacing with neural circuits.
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Encéfalo , Optogenética , Encéfalo/fisiologíaRESUMEN
Characterization of photovoltaic (PV) module materials throughout different stages of service life is crucial to understanding and improving the durability of these materials. Currently the large-scale of PV modules (>1 m2) is imbalanced with the small-scale of most materials characterization tools (≤1 cm2). Furthermore, understanding degradation mechanisms often requires a combination of multiple characterization techniques. Here, we present adaptations of three standard materials characterization techniques to enable mapping characterization over moderate sample areas (≥25 cm2). Contact angle, ellipsometry, and UV-vis spectroscopy are each adapted and demonstrated on two representative samples: a commercial multifunctional coating for PV glass and an oxide combinatorial sample library. Best practices are discussed for adapting characterization techniques for large-area mapping and combining mapping information from multiple techniques.
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Técnicas Químicas Combinatorias , Suministros de Energía Eléctrica , Energía Solar , Vidrio/química , Ensayo de MaterialesRESUMEN
We report successful growth of a uniform and scalable nanocomposite film of Fe2O3 nanorods (NRs) and NiOx nanoparticles (NPs), their properties and application for enhanced solar water reduction in neutral pH water on the surface of p-Si photocathodes.
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We report a facile and large-scale fabrication of three-dimensional (3D) ZnO/CuO heterojunction branched nanowires (b-NWs) and their application as photocathodes for photoelectrochemical (PEC) solar hydrogen production in a neutral medium. Using simple, cost-effective thermal oxidation and hydrothermal growth methods, ZnO/CuO b-NWs are grown on copper film or mesh substrates with various ZnO and CuO NWs sizes and densities. The ZnO/CuO b-NWs are characterized in detail using high-resolution scanning and transmission electron microscopies exhibiting single-crystalline defect-free b-NWs with smooth and clean surfaces. The correlation between electrode currents and different NWs sizes and densities are studied in which b-NWs with longer and denser CuO NW cores show higher photocathodic current due to enhanced reaction surface area. The ZnO/CuO b-NW photoelectrodes exhibit broadband photoresponse from UV to near IR region, and higher photocathodic current than the ZnO-coated CuO (core/shell) NWs due to improved surface area and enhanced gas evolution. Significant improvement in the photocathodic current is observed when ZnO/CuO b-NWs are grown on copper mesh compared to copper film. The achieved results offer very useful guidelines in designing b-NWs mesh photoelectrodes for high-efficiency, low-cost, and flexible PEC cells using cheap, earth-abundant materials for clean solar hydrogen generation at large scales.
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The lack of a high capacity hydrogen storage material is a major barrier to the implementation of the hydrogen economy. To accelerate discovery of such materials, we have developed a high-throughput workflow for screening of hydrogen storage materials in which candidate materials are synthesized and characterized via highly parallel ball mills and volumetric gas sorption instruments, respectively. The workflow was used to identify mixed imides with significantly enhanced absorption rates relative to Li2Mg(NH)2. The most promising material, 2LiNH2:MgH2 + 5 atom % LiBH4 + 0.5 atom % La, exhibits the best balance of absorption rate, capacity, and cycle-life, absorbing >4 wt % H2 in 1 h at 120 °C after 11 absorption-desorption cycles.