Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control

Although the performance of lithium ion-batteries continues to improve, their energy density and cycle life remain insufficient for applications in consumer electronics, transport and large-scale renewable energy storage. Silicon has a large charge storage capacity and this makes it an attractive anode material, but pulverization during cycling and an unstable solid-electrolyte interphase has limited the cycle life of silicon anodes to hundreds of cycles. Here, we show that anodes consisting of an active silicon nanotube surrounded by an ion-permeable silicon oxide shell can cycle over 6,000 times in half cells while retaining more than 85% of their initial capacity. The outer surface of the silicon nanotube is prevented from expansion by the oxide shell, and the expanding inner surface is not exposed to the electrolyte, resulting in a stable solid-electrolyte interphase. Batteries containing these double-walled silicon nanotube anodes exhibit charge capacities approximately eight times larger than conventional carbon anodes and charging rates of up to 20C (a rate of 1C corresponds to complete charge or discharge in one hour).     

Petrological and geochemical mass-balance equations: an algorithm for least-square fitting and general error analysis

Least-square fitting of petrological and geochemical overdetermined linear systems is carried out by means of a rapidly converging algorithm which allows a general treatment of coefficient uncertainties. Both constrained and unconstrained solutions are presented. The modal analysis of lunar rock 10022 and stoichiometric coefficients for two coronitic reactions are so determined, as an example, from application of the proposed procedure to available chemical analyses.     

Unraveling the Physics of Vertical Organic Field Effect Transistors through Nanoscale Engineering of a Self-Assembled Transparent Electrode

While organic transistors' performances are continually pushed to achieve lower power consumption, higher working frequencies, and higher current densities, a new type of organic transistors characterized by a vertical architecture offers a radically different design approach to outperform its traditional counterparts. Naturally, the distinct vertical architecture gives way to different governing physical ground rules and structural key features such as the need for an embedded transparent electrode. In this paper, we make use of a zero-frequency electric field-transparent patterned electrode produced through block-copolymer self-assembly based lithography to control the performances of the vertical organic field effect transistor (VOFET) and to study its governing physical mechanisms. Unlike other VOFET structures, this design, involving well-defined electrode architecture, is fully tractable, allowing for detailed modeling, analysis, and optimization. We provide for the first time a complete account of the physics underpinning the VOFET operation, considering two complementary mechanisms: the virtual contact formation (Schottky barrier lowering) and the induced potential barrier (solid-state triode-like shielding). We demonstrate how each mechanism, separately, accounts for the link between controllable nanoscale structural modifications in the patterned electrode and the VOFET performances. For example, the ON/OFF current ratio increases by up to 2 orders of magnitude when the perforations aspect ratio (height/width) decreases from ～0.2 to ～0.1. The patterned electrode is demonstrated to be not only penetrable to zero-frequency electric fields but also transparent in the visible spectrum, featuring uniformity, spike-free structure, material diversity, amenability with flexible surfaces, low sheet resistance (20-2000 Ω sq(-1)) and high transparency (60-90%). The excellent layer transparency of the patterned electrode and the VOFET's exceptional electrical performances make them both promising elements for future transparent and/or efficient organic electronics.     

Functional Free‐Standing Graphene Honeycomb Films

Fabricating free‐standing, three‐dimensional (3D) ordered porous graphene structure can service a wide range of functional materials such as environmentally friendly materials for antibacterial medical applications and efficient solar harvesting devices. A scalable solution processable strategy is developed to create such free‐standing hierarchical porous structures composed of functionalized graphene sheets via an “on water spreading” method. The free‐standing film shows a large area uniform honeycomb structure and can be transferred onto any substrate of interest. The graphene‐based free‐standing honeycomb films exhibit superior broad spectrum antibacterial activity as confirmed using green fluorescent protein labeled Pseudomonas aeruginosa PAO1 and Escherichia coli as model pathogens. Functional nanoparticles such as titanium dioxide (TiO₂) nanoparticles can be easily introduced into conductive graphene‐based scaffolds by premixing. The formed composite honeycomb film electrode shows a fast, stable, and completely reversible photocurrent response accompanying each switch‐on and switch‐off event. The graphene‐based honeycomb scaffold enhances the light‐harvesting efficiency and improves the photoelectric conversion behavior; the photocurrent of the composite film is about two times as high as that of the pure TiO₂ film electrode. Such composite porous films combining remarkably good electrochemical performance of graphene, a large electrode/electrolyte contact area, and excellent stability during the photo‐conversion process hold promise for further applications in water treatment and solar energy conversion.     

Reusable Polyacrylonitrile-Sulfur Extractor of Heavy Metal Ions from Wastewater

Mercury, lead, and cadmium are among the most toxic and carcinogenic heavy metal ions (HMIs), posing serious threats to the sustainability of aquatic ecosystems and public health. There is an urgent need to remove these ions from water by a cheap but green process. Traditional methods have insufficient removal efficiency and reusability. Structurally robust, large surface-area adsorbents functionalized with high-selectivity affinity to HMIs are attractive filter materials. Here, an adsorbent prepared by vulcanization of polyacrylonitrile (PAN), a nitrogen-rich polymer, is reported, giving rise to PAN-S nanoparticles with cyclic π-conjugated backbone and electronic conductivity. PAN-S can be coated on ultra-robust melamine (ML) foam by simple dipping and drying. In agreement with hard/soft acid/base theory, N- and S-containing soft Lewis bases have strong binding to Hg²⁺, Pb²⁺, Cu²⁺, and Cd²⁺, with extraordinary capture efficiency and performance stability. Furthermore, the used filters, when collected and electrochemically biased in a recycling bath, can release the HMIs into the bath and electrodeposit on the counter-electrode as metallic Hg⁰, Pb⁰, Cu⁰, and Cd⁰, and the PAN-S@ML filter can then be reused at least 6 times as new. The electronically conductive PAN-S@ML filter can be fabricated cheaply and holds promise for scale-up applications.     

The Jama Legal Narrative Part I: The JAMA Model and Narrative Interpretation Patterns

For the purposes of starting to tackle, within artificial intelligence (AI), the narrative aspects of legal narratives in a criminal evidence perspective, traditional AI models of narrative understanding can arguably supplement extant models of legal narratives from the scholarly literature of law, jury studies, or the semiotics of law. Not only: the literary (or cinematic) models prominent in a given culture impinge, with their poetic conventions, on the way members of the culture make sense of the world. This shows glaringly in the sample narrative from the Continent-the Jama murder, the inquiry, and the public outcry-we analyse in this paper. Apparently in the same racist crime category as the case of Stephen Lawrence's murder (in Greenwich on 22 April 1993) with the ensuing still current controversy in the UK, the Jama case (some 20 years ago) stood apart because of a very unusual element: the eyewitnesses identifying the suspects were a group of football referees and linesmen eating together at a restaurant, and seeing the sleeping man as he was set ablaze in a public park nearby. Professional background as witnesses-cum-factfinders in a mass sport, and public perceptions of their required characteristics, couldn't but feature prominently in the public perception of the case, even more so as the suspects were released by the magistrate conducting the inquiry. There are sides to this case that involve different expected effects in an inquisitorial criminal procedure system from the Continent, where an investigating magistrate leads the inquiry and prepares the prosecution case, as opposed to trial by jury under the Anglo-American adversarial system. In the JAMA prototype, we tried to approach the given case from the coign of vantage of narrative models from AI.     

Optimization of Potassium Dinitramide Preparation

The synthesis of potassium dinitramide (KDN), an intermediate in the ammonium dinitramide (ADN) synthesis, was optimized to reduce the costs of the ADN synthesis in order to facilitate competitiveness of this oxidizer with ammonium perchlorate (AP). The optimal conditions for the synthesis of KDN like feedstock molar ratio, nitration time, and temperature were determined. KDN was obtained in ca. 48 % yield. The modifications introduced allowed to reduce feedstock consumption and energy intensity of the process.     

Synthetic Chain Terminators Off‐Load Intermediates from a Type I Polyketide Synthase

Modular biocatalysis is responsible for the generation of countless bioactive products and its mining remains a major focus for drug discovery purposes. One of the enduring hurdles is the isolation of biosynthetic intermediates in a readily‐analysed form. We prepared a series of nonhydrolysable pantetheine and N‐acetyl cysteamine mimics of the natural (methyl)malonyl extender units recruited for polyketide formation. Using these analogues as competitive substrates, we were able to trap and off‐load diketide and triketide species directly from an in vitro reconstituted type I polyketide synthase, the 6‐deoxyerythronolide B synthase 3 (DEBS3). The putative intermediates, which were extracted in organic solvent and characterised by LC‐HR‐ESI‐MS, are the first of their kind and prove that small‐molecule chain terminators can be used as convenient probes of the biosynthetic process.     

Use of UV-C treatments to maintain quality and extend the shelf life of green fresh-cut bell pepper (Capsicum annuum L.)

Abstract: The objective of this work was to select a Ultraviolet‐C (UV‐C) treatment for fresh‐cut mature green bell pepper, and to evaluate the effect of its combination with refrigeration on quality maintenance. Bell pepper sticks were treated with 0, 3, 10, or 20 kJ/m² UV‐C in the outer (O), inner (I), or both sides of the pericarp (I/O) and stored for 8 d at 10 °C. During the first 5 d of storage, all UV‐C treatments reduced deterioration as compared to the control. The treatment with 20 kJ/m² I/O was the most effective to reduce deterioration, and was used for further evaluations. In a second group of experiments, mature green bell pepper sticks were treated with 20 kJ/m² I/O, stored at 5 °C for 7 or 12 d and assessed for physical and chemical analysis, and microbiological quality. UV‐C‐treated fruit showed lower exudates and shriveling than the control. UV exposure also reduced decay, tissue damage, and electrolyte leakage. After 12 d at 5 °C, UV‐C irradiated peppers remained firmer and had higher resistance to deformation than the control. The UV‐C treatments also reduced weight loss and pectin solubilization. UV‐C exposure decreased the counts of mesophile bacteria and molds, and did not affect acidity or sugars. UV‐C‐treated fruit stored for 0 or 7 d at 5 °C did not show major differences in antioxidants from the control as measured against DPPH^? or ABTS^?+ radicals. Results suggest that UV‐C exposure is useful to maintain quality of refrigerated fresh‐cut green pepper. Practical Application: Exposure to UV‐C radiation before packing and refrigeration could be a useful nonchemical alternative to maintain quality and reduce postharvest losses in the fresh‐cut industry.