Dynamic Covalent Synthesis of Crystalline Porous Graphitic Frameworks

Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability. Insertion of well-defined, evenly spaced nanoscale pores into the two-dimensional (2D) layers of graphene invokes exciting properties due to the modulation of its electronic band gaps and surface functionalities. A bottom-up synthesis approach to such porous graphitic frameworks (PGFs) is appealing but also remains a great challenge. The current methods of building covalent organic frameworks rely on a small collection of thermodynamically reversible reactions. Such reactions are, however, inadequate in generating a fully annulated aromatic skeleton in PGFs. With the discovery of dynamic pyrazine formation, we succeeded in applying this linking chemistry to obtain a crystalline PGF material, which has displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries. We envision that the demonstrated success will open the door to a wide array of fully annulated 2D porous frameworks, which hold immense potential for clean energy applications. We report the unusual dynamic characteristics of the C=N bonds in the pyrazine ring promoted under basic aqueous conditions, which enables the successful synthesis of two-dimensional porous graphitic frameworks (PGFs) featuring fully annulated aromatic skeletons and periodic pores. The PGF displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries, far outperforming the amorphous counterparts in terms of capacity and cycle stability

Optimization of Picosecond Laser Parameters for Surface Treatment of Composites Using a Design of Experiments (DOE) Approach

Based on guidelines from the Federal Aviation Administration, research supported by the NASA Advanced Composites Project is investigating methods to improve process control for surface preparation and pre-bond surface characterization on aerospace composite structures. The overall goal is to identify high fidelity, rapid, and reproducible surface treatments and surface characterization methods to reduce the uncertainty associated with the bonding process. The desired outcome is a more reliable bonded airframe structure, and to reduce time to achieve certification. In this work, a design of experiments (DoE) approach was conducted to determine optimum laser ablation conditions using a pulsed laser source with a nominal pulse width of 10 picoseconds. The laser power, frequency, scan speed, and number of passes (1 or 2) were varied within the laser system operating boundaries. Aerospace structural carbon fiber reinforced composites (Torayca 3900-2/T800H) were laser treated, then characterized for contamination, and finally bonded for mechanical testing. Pre-bond characterization included water contact angle (WCA) using a handheld device, ablation depth measurement using scanning electron microscopy (SEM), and silicone contamination measurement using laser induced breakdown spectroscopy (LIBS). In order to accommodate the large number of specimens in the DoE, a rapid-screening, double cantilever beam (DCB) test specimen configuration was devised based on modifications to ASTM D5528. Specimens were tested to assess the failure modes observed under the various laser surface treatment parameters. The models obtained from this DoE indicated that results were most sensitive to variation in the average laser power. Excellent bond performance was observed with nearly 100% cohesive failure for a wide range of laser parameters. Below about 200 mW, adhesive failure was observed because contamination was left on the surface. For laser powers greater than about 600 mW, large amounts of fiber were exposed, and the failure mode was predominately fiber tear

Evaluating the mineral nutrient status of fresh pasture herbage using laser-induced breakdown spectroscopy

Comprehensive determination of the mineral nutrient status of pasture or horticultural crops currently requires leaf or herbage samples to be harvested and taken to a laboratory for analysis, which is both labour-intensive and time-consuming. This study examined the potential of laser-induced breakdown spectroscopy (LIBS) to provide immediate, in-field assessment of the mineral nutrient status of standing plants. Success would offer the prospects of spatially and temporally improved knowledge of plant status and of real-time remediation of nutrient deficiency. The mineral nutrient status of fresh pasture herbage has been evaluated using an Applied Photonics Ltd？ LIBS-6 system, comprising a Qswitched Nd:YAG laser, a SpectroModule-6 spectrometer (covering wavelengths in the range ~185 – 1064 nm) and an ICE 450 water-cooled Laser power supply. LIBS spectra obtained from the fresh pasture samples were collected with the aim of determining the nutrient status of the herbage. An enclosed Modular Sample Chamber housed the Qswitched Nd:YAG laser, generating energy in the near infrared region at λ = 1064nm. The laser power was set to 100mW per pulse. Samples of approximately 50g of fresh ryegrass and ryegrass/clover mixed pasture were loaded into a sample holder which allowed a flat ‗carpet‘ of individual leaves to be presented at a relatively uniform distance from the laser. The optimum vertical distance between sample and laser was determined by maximising spectra amplitudes. Automated control of the translation stage supporting the sample holder was used to ensure each shot of the laser was acquired from a fresh location. Spectrum sets comprising both 100 individual spectra and 100 shot accumulated spectra were obtained from each sample under both air and under the inert gas, argon. Following the spectral analysis of the fresh pasture, each sample was sent to a commercial laboratory for standard nutrient analysis, providing elementary composition on the most common plant elements (N, P, K, S, Ca, Mg, Na, Fe, Mn, Zn, Cu and B). Once standard nutrient analysis was completed a second set of spectra was taken from tablets formed from compressed dried ground powder remaining after laboratory analysis. To date, initial results from simple chemometric analysis have shown limited success in predicting the nutrient content of fresh pasture with slightly improved results in estimating tablet composition. While initial analyses have concentrated on trends and correlations between actual spectra and laboratory analysis, known emission spectra, have for the meantime, been ignored. Further in-depth analysis using more robust chemometric analysis, utilizing known emission spectra and adjusting for variations in plasma intensity are currently underway and are expected to improve the accuracy of composition measurement

Optimizing Service Differentiation Scheme with Sized-based Queue Management in DiffServ Networks

In this paper we introduced Modified Sized-based Queue Management as a dropping scheme that aims to fairly prioritize and allocate more service to VoIP traffic over bulk data like FTP as the former one usually has small packet size with less impact to the network congestion. In the same time, we want to guarantee that this prioritization is fair enough for both traffic types. On the other hand we study the total link delay over the congestive link with the attempt to alleviate this congestion as much as possible at the by function of early congestion notification. Our M-SQM scheme has been evaluated with NS2 experiments to measure the packets received from both and total link-delay for different traffic. The performance evaluation results of M-SQM have been validated and graphically compared with the performance of other three legacy AQMs (RED, RIO, and PI). It is depicted that our M-SQM outperformed these AQMs in providing QoS level of service differentiation.Comment: 10 pages, 9 figures, 1 table, Submitted to Journal of Telecommunication

Advances in bioleaching as a sustainable method for metal recovery from e-waste:A review

Electronic waste (e-waste) accumulation on earth is a serious environmental challenge. The need for heavy metal recovery, together with the profitability of precious and base metals, are strong incentives for researchers to find a sustainable method for metal recovery from e-waste. The scientific community is trying to improve the efficiency of metal recovery from e-wastes using bioleaching, a more sustainable method in comparison to traditional methods. In this review, available methods and the kinetic models that describe the bioleaching processes, and also their limitations, are reviewed. In addition, the application of new approaches to understand how the contribution of microorganisms and their genetic modification can affect the processes, are reviewed.</p

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