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Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation. 相似文献
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Molina-Sabio M Sánchez-Montero MJ Juarez-Galan JM Salvador F Rodríguez-Reinoso F Salvador A 《The journal of physical chemistry. B》2006,110(25):12360-12364
Two series of activated carbon have been prepared by reaction of a char (from olive stones) with supercritical water (SCW) with the objective of studying the effect of temperature and residence time on the development of porosity. The results have been compared with those obtained using the same char but with classical activation with steam. Both procedures develop porosity, but (i) the reaction rate is critical in the development of porosity for steam but not for SCW activation, and (ii) SCW activation produces a larger development of microporosity at low degrees of burnoff, whereas steam produces more meso- and macroporosity. The differences have been explained by assuming that the mechanism for the carbon-water reaction is common but the transport properties of water in the supercritical state are more favorable to facilitate the access of water to the interior of the char particles. In contrast, when steam is used for the activation of the char, the diffusion of the molecules cannot keep up with the chemical rate and, consequently, the reaction is preferentially taking place at the most accessible surface sites, thus facilitating the development of larger pores and the widening of microporosity. 相似文献
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We analyse different error propagation mechanisms for conservativeand nonconservative time-integrators of nonlinear Schrödingerequations. We use a geometric approach based on interpretingwaves as relative equilibria. 相似文献
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Nikky Kortbeek Aleida Braaksma Ferry HF Smeenk Piet JM Bakker Richard J Boucherie 《The Journal of the Operational Research Society》2015,66(7):1061-1076
The design and operations of inpatient care facilities are typically largely historically shaped. A better match with the changing environment is often possible, and even inevitable due to the pressure on hospital budgets. Effectively organizing inpatient care requires simultaneous consideration of several interrelated planning issues. Also, coordination with upstream departments like the operating theatre and the emergency department is much-needed. We present a generic analytical approach to predict bed census on nursing wards by hour, as a function of the Master Surgical Schedule and arrival patterns of emergency patients. Along these predictions, insight is gained on the impact of strategic (ie, case mix, care unit size, care unit partitioning), tactical (ie, allocation of operating room time, misplacement rules), and operational decisions (ie, time of admission/discharge). The method is used in the Academic Medical Center Amsterdam as a decision-support tool in a complete redesign of the inpatient care operations. 相似文献
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A new cryogenic integrative air sampler (patent application number 08/00669), able to overcome many of the limitations in current volatile organic compounds and odour sampling methodologies is presented. The sample is spontaneously collected in a universal way at 15 mL/min, selectively dried (reaching up to 95% of moisture removal) and stored under cryogenic conditions. The sampler performance was tested under time weighted average (TWA) conditions, sampling 100 L of air over 5 days for determination of NH3, H2S, and benzene, toluene, ethylbenzene and xylenes (BTEX) in the ppmv range. Recovery was 100% (statistically) for all compounds, with a concentration factor of 5.5. Furthermore, an in-field evaluation was done by monitoring the TWA inmission levels of BTEX and dimethylethylamine (ppbv range) in an urban area with the developed technology and comparing the results with those monitored with a commercial graphitised charcoal diffusive sampler. The results obtained showed a good statistical agreement between the two techniques. 相似文献
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