Three Dimensionally Ordered Mesoporous Carbon as a Stable,High‐Performance Li–O2 Battery Cathode

Enabled by the reversible conversion between Li₂O₂ and O₂, Li–O₂ batteries promise theoretical gravimetric capacities significantly greater than Li‐ion batteries. The poor cycling performance, however, has greatly hindered the development of this technology. At the heart of the problem is the reactivity exhibited by the carbon cathode support under cell operation conditions. One strategy is to conceal the carbon surface from reactive intermediates. Herein, we show that long cyclability can be achieved on three dimensionally ordered mesoporous (3DOm) carbon by growing a thin layer of FeO_x using atomic layer deposition (ALD). 3DOm carbon distinguishes itself from other carbon materials with well‐defined pore structures, providing a unique material to gain insight into processes key to the operations of Li–O₂ batteries. When decorated with Pd nanoparticle catalysts, the new cathode exhibits a capacity greater than 6000 mAh g_carbon^?1 and cyclability of more than 68 cycles.     

Identification of mechanisms of toxic action for skin sensitisation using a SMARTS pattern based approach

Skin sensitisation is a key endpoint under REACH as it is costly and its assessment currently has a high dependency on animal testing. In order to reduce both the cost and the numbers of animals tested, it is likely that (quantitative) structure–activity relationships ((Q)SAR) and read-across methods will be utilised as part of intelligent testing strategies. The majority of skin sensitisers elicit their effect via covalent bond formation with skin proteins. These reactions have been understood in terms of well defined nucleophilic–electrophilic reaction chemistry. Thus, a first step in (Q)SAR analysis is the assignment of a chemical's potential mechanism of action enabling it to be placed in an appropriate reactivity domain. The aim of this study was to design a series of SMARTS patterns capable of defining these reactivity domains. This was carried out using a large database of local lymph node assay (LLNA) results that had had potential mechanisms of action assigned to them using expert knowledge. A simple algorithm was written enabling the SMARTS patterns to be used to screen a database of SMILES strings. The SMARTS patterns were then evaluated using a second, smaller, test set of LLNA results which had also had potential mechanisms of action assigned by experts. The results showed that the SMARTS patterns provided an excellent method of identifying potential electrophilic mechanisms. The findings are supported, in part, by molecular orbital calculations which confirm assignment of reactive mechanism of action. The ability to define a chemical's potential reaction mechanism is likely to be of significant benefit to regulators and risk assessors as it enables category formation and subsequent read-across to be performed.     

A parameter-uniform Schwarz method for a coupled system of reaction–diffusion equations

We consider an arbitrarily sized coupled system of one-dimensional reaction–diffusion problems that are singularly perturbed in nature. We describe an algorithm that uses a discrete Schwarz method on three overlapping subdomains, extending the method in [H. MacMullen, J.J.H. Miller, E. O’Riordan, G.I. Shishkin, A second-order parameter-uniform overlapping Schwarz method for reaction-diffusion problems with boundary layers, J. Comput. Appl. Math. 130 (2001) 231–244] to a coupled system. On each subdomain we use a standard finite difference operator on a uniform mesh. We prove that when appropriate subdomains are used the method produces ε-uniform results. Furthermore we improve upon the analysis of the above-mentioned reference to show that, for small ε, just one iteration is required to achieve the expected accuracy.     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

Efficient CO2 Removal for Ultra‐Pure CO Production by Two Hybrid Ultramicroporous Materials

Removal of CO₂ from CO gas mixtures is a necessary but challenging step during production of ultra‐pure CO as processed from either steam reforming of hydrocarbons or CO₂ reduction. Herein, two hybrid ultramicroporous materials (HUMs), SIFSIX‐3‐Ni and TIFSIX‐2‐Cu‐i , which are known to exhibit strong affinity for CO₂, were examined with respect to their performance for this separation. The single‐gas CO sorption isotherms of these HUMs were measured for the first time and are indicative of weak affinity for CO and benchmark CO₂/CO selectivity (>4000 for SIFSIX‐3‐Ni ). This prompted us to conduct dynamic breakthrough experiments and compare performance with other porous materials. Ultra‐pure CO (99.99 %) was thereby obtained from CO gas mixtures containing both trace (1 %) and bulk (50 %) levels of CO₂ in a one‐step physisorption‐based separation process.     

Arithmetic in generalized Artin-Schreier extensions of k(x)

If k is a perfect field of characteristic p ≠ 0 and k(x) is the rational function field over k, it is possible to construct cyclic extensions K_n over k(x) such that [K : k(x)] = pⁿ using the concept of Witt vectors. This is accomplished in the following way; if [β₁, β₂,…, β_n] is a Witt vector over k(x) = K₀, then the Witt equation $\text{y}{}^{\mathrm{p}}\text{?}\text{y}\text{= β}$ generates a tower of extensions through $\text{K}{}_{\mathrm{i}}\text{= K}{}_{\mathrm{i?1}}\text{(}\text{y}{}_{\mathrm{i}}\text{)}$ where $\text{y}\text{= [}\text{y}{}_1\text{,}\text{y}{}_2\text{,…,}\text{y}{}_{\mathrm{n}}\text{]}$. In this paper, it is shown that there exists an alternate method of generating this tower which lends itself better for further constructions in K_n. This alternate generation has the form K_i = K_i?1(y_i); y_i^p ? y_i = B_i, where, as a divisor in K_i?1, B_i has the form . In this form q is prime to Πp_j^λ_j and each λ_j is positive and prime to p. As an application of this, the alternate generation is used to construct a lower-triangular form of the Hasse-Witt matrix of such a field K_n over an algebraically closed field of constants.