Highly Porous Materials as Tunable Electrocatalysts for the Hydrogen and Oxygen Evolution Reaction

The facile preparation of highly porous, manganese doped, sponge‐like nickel materials by salt melt synthesis embedded into nitrogen doped carbon for electrocatalytic applications is shown. The incorporation of manganese into the porous structure enhances the nickel catalyst's activity for the hydrogen evolution reaction in alkaline solution. The best catalyst demonstrates low onset overpotential (0.15 V) for the hydrogen evolution reaction along with high current densities at higher potentials. In addition, the possibility to alter the electrocatalytic properties of the materials from the hydrogen to oxygen evolution reaction by simple surface oxidation is shown. The surface area increases up to 1200 m²g^?1 after mild oxidation accompanied by the formation of nickel oxide on the surface. A detailed analysis shows a synergetic effect of the oxide formation and the material's surface area on the catalytic performance in the oxygen evolution reaction. In addition, the synthesis of cobalt doped sponge‐like nickel materials is also delineated, demonstrating the generality of the synthesis. The facile salt melt synthesis of such highly porous metal based materials opens new possibilities for the fabrication of diverse electrode nanostructures for electrochemical applications.     

Nongeminate and Geminate Recombination in PTB7:PCBM Solar Cells

A combination of transient photovoltage (TPV), voltage dependent charge extraction (CE), and time delayed collection field (TDCF) measurements is applied to poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b']dithiophene‐2,6‐diyl] [3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl] thieno[3,4‐b]thiophenediyl]] (PTB7):[6,6]‐phenyl‐C71‐butyric acid (PC₇₁BM) bulk heterojunction solar cells to analyze the limitations of photovoltaic performance. Devices are processed from pure chlorobenzene (CB) solution and a subset is optimized with 1,8‐diiodooctane (DIO) as co‐solvent. The dramatic changes in device performance are discussed with respect to the dominating loss processes. While in the devices processed from CB solution severe geminate and nongeminate recombination is observed, the use of DIO facilitates efficient polaron pair dissociation and minimizes geminate recombination. Thus, from the determined charge carrier decay rate under open circuit conditions and the voltage dependent charge carrier densities n(V), the nongeminate loss current J_loss of the samples with DIO alone enables the reconstruction of the current/voltage (j/V) characteristics across the whole operational voltage range. Geminate and nongeminate losses are considered to describe the j/V response of cells prepared without additive, but lead to a clearly overestimated device performance. The deviation between measured and reconstructed j/V characteristics is attributed to trapped charges in isolated domains of pure fullerene phases.     

Fast Switching ITO Free Electrochromic Devices

Indium‐doped tin oxide free electrochromic devices are prepared by coating electrochromic polymers onto polyethylene terephthalate substrates encompassing two different silver grids as electrodes. One design comprises a flexoprinted highly conductive silver grid electrode, yielding electrochromic devices with a response time of 2 s for an optical contrast of 27%. The other design utilizes an embedded silver grid electrode whereupon response times of 0.5 s for a 30% optical contrast are realized when oxidizing the device. A commercially available conductive poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate acid) formulation (PEDOT:PSS) is coated onto the silver grids as a charge balancing polymer, and is in this setting found to be superior to a polypyrrole previously employed in electrochromic devices. In addition, the PEDOT:PSS layer increases the conductivity in the hexagonal grid structure.     

X-ray based tools for the investigation of buried interfaces in organic electronic devices

X-ray reflectivity combined with grazing incidence diffraction is a valuable tool for investigating organic multilayer structures that can be used in devices. We focus on a bilayer stack consisting of two materials (poly-(3-hexylthiophene)) (P3HT) and poly-(4-styrenesulfonic acid) (PSSA) spin cast from orthogonal solvents (water in the case of PSSA and chloroform or toluene for P3HT). X-ray reflectivity is used to determine the thickness of all layers as well as the roughness of the organic–organic hetero-interface and the P3HT surface. The surface roughness is found to be consistent with the results of atomic force microscopy measurements. For the roughness of P3HT/PSSA interface, we observe a strong dependence on the solvent used for P3HT deposition. The solvent also strongly impacts the texturing of the P3HT crystallites as revealed by grazing incidence diffraction. When applying the various PSSA/P3HT multilayers in organic thin-film transistors, we find an excellent correlation between the determined interface morphology, structure and the device performance.     

Diindenoperylene derivatives: A model to investigate the path from molecular structure via morphology to solar cell performance

Efficient organic electronic devices require a detailed understanding of the relation between molecular structure, thin film growth, and device performance, which is only partially understood at present. Here, we show that small changes in molecular structure of a donor absorber material lead to significant changes in the intermolecular arrangement within organic solar cells. For this purpose, phenyl rings and propyl side chains are fused to the diindenoperylene (DIP) molecule. Grazing incidence X-ray diffraction and variable angle spectroscopic ellipsometry turned out to be a powerful combination to gain detailed information about the thin film growth. Planar and bulk heterojunction solar cells with C60 as acceptor and the DIP derivatives as donor are fabricated to investigate the influence of film morphology on the device performance. Due to its planar structure, DIP is found to be highly crystalline in pristine and DIP:C60 blend films while its derivatives grow liquid-like crystalline. This indicates that the molecular arrangement is strongly disturbed by the steric hindrance induced by the phenyl rings. The high fill factor (FF) of more than 75% in planar heterojunction solar cells of the DIP derivatives indicates excellent charge transport in the pristine liquid-like crystalline absorber layers. However, bulk heterojunctions of these materials surprisingly result in a low FF of only 54% caused by a weak phase separation and thus poor charge carrier percolation paths due to the lower ordered thin film growth. In contrast, crystalline DIP:C60 heterojunctions lead to high FF of up to 65% as the crystalline growth induces better percolation for the charge carriers. However, the major drawback of this crystalline growth mode is the nearly upright standing orientation of the DIP molecules in both pristine and blend films. This arrangement results in low absorption and thus a photocurrent which is significantly lower than in the DIP derivative devices, where the liquid-like crystalline growth leads to a more horizontal molecular alignment. Our results underline the complexity of the molecular structure-device performance relation in organic semiconductor devices.     

A survey of autonomic networking architectures: towards a Unified Management Framework

Academic and industrial research initiatives have sought to make fully autonomic networks a reality. Some of these initiatives pursued a holistic approach, while others focused on setting up functionalities for specific networking domains. These efforts did not succeed in being extensively deployed, because the goals of network operators were not satisfactorily met. These goals include unification of management operations, enablement of end‐to‐end management and enhancement of the overall system performance in a trusted way, while reducing management cost. In this paper, we analyse a set of existing autonomic management architectures and frameworks with respect to a selected set of criteria. We then identify missing parts and challenges and propose a framework to unify the most promising attributes towards a novel approach of realization of autonomic networking management. We call this proposal Unified Management Framework (UMF). Copyright © 2013 John Wiley & Sons, Ltd.     

A Bio-Conjugated Fullerene as a Subcellular-Targeted and Multifaceted Phototheranostic Agent

Fullerenes are candidates for theranostic applications because of their high photodynamic activity and intrinsic multimodal imaging contrast. However, fullerenes suffer from low solubility in aqueous media, poor biocompatibility, cell toxicity, and a tendency to aggregate. C₇₀@lysozyme is introduced herein as a novel bioconjugate that is harmless to a cellular environment, yet is also photoactive and has excellent optical and optoacoustic contrast for tracking cellular uptake and intracellular localization. The formation, water-solubility, photoactivity, and unperturbed structure of C₇₀@lysozyme are confirmed using UV-visible and 2D ¹H, ¹⁵N NMR spectroscopy. The excellent imaging contrast of C₇₀@lysozyme in optoacoustic and third harmonic generation microscopy is exploited to monitor its uptake in HeLa cells and lysosomal trafficking. Last, the photoactivity of C₇₀@lysozyme and its ability to initiate cell death by means of singlet oxygen (¹O₂) production upon exposure to low levels of white light irradiation is demonstrated. This study introduces C₇₀@lysozyme and other fullerene-protein conjugates as potential candidates for theranostic applications.     

Analog VLSI Circuits for Competitive Learning Networks

An investigation is made concerning implementations of competitive learning algorithms in analog VLSI circuits and systems. Analog and low power digital circuits for competitive learning are currently important for their applications in computationally-efficient speech and image compression by vector quantization, as required for example in portable multi-media terminals. A summary of competitive learning models is presented to indicate the type of VLSI computations required, and the effects of weight quantization are discussed. Analog circuit representations of computational primitives for learning and evaluation of distortion metrics are discussed. The present state of VLSI implementations of hard and soft competitive learning algorithms are described, as well as those for topological feature maps. Tolerance of learning algorithms to observed analog circuit properties is reported. New results are also presented from simulations of frequency-sensitive and soft competitive learning concerning sensitivity of these algorithms to precision in VLSI learning computations. Applications of these learning algorithms to unsupervised feature extraction and to vector quantization of speech and images are also described.     

Performance of uprated substations in contaminated environments

Uprated substations have proven to be a viable economic alternative to rebuilding in order to increase power system capacity. The key economic factor in uprated designs is the use of lower than traditional insulation margins in high voltage substations. The experience of these uprated substations has been good and insulation design procedures for uprated substations have been developed to show other engineers how to take advantage of this design alternative. While these design procedures and other publications including the results of actual tests have given ample evidence of the success of the uprated designs, it has been noted that several areas need more study and testing. Among those areas which need further study are the effects of the dynamic forces caused by higher fault currents in the uprated substations and the ability of the reduced creepage distances of the uprated design to withstand pollution severity. This study covers the pollution severity issue by examining the results of flashover tests on the uprated substation insulators under various contamination conditions. The tests, which were done at the EPRI Power Deliver Center at Lenox, USA, are believed to be the only flashover tests ever conducted with uprated insulators. As might be expected, the uprated design is shown to be very sensitive to pollution severity. Sites chosen for uprating should include a pollution severity assessment as part of the design review