22 research outputs found

    Synthesis, studies and fuel cell performance of “core–shell” electrocatalysts for oxygen reduction reaction based on a PtNix carbon nitride “shell” and a pyrolyzed polyketone nanoball “core”

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    This report describes a new class of "core-shell" electrocatalysts for oxygen reduction reaction (ORR) processes for application in Proton Exchange Membrane Fuel Cells (PEMFCs). The electrocatalysts are obtained by supporting a "shell" consisting of PtNix alloy nanoparticles embedded into a carbon nitride matrix (indicated as PtNix-CN) on a "core" of pyrolyzed polyketone nanoballs, labeled 'STp'. ST(p)s are obtained by the sulfonation and pyrolysis of a precursor consisting of XC-72R carbon nanoparticles wrapped by polyketone (PK) fibers. The ST(p)s are extensively characterized in terms of the chemical composition, thermal stability, degree of graphitization and morphology. The "core-shell" ORR electrocatalysts are prepared by the pyrolysis of precursors obtained impregnating the STp "cores" with a zeolitic inorganic-organic polymer electrolyte (Z-IOPE) plastic material. The electrochemical performance of the electrocatalysts in the ORR is tested "in situ" by single fuel cell tests. The interplay between the chemical composition, the degree of graphitization of both PtNix-CN "shell" and STpS "cores", the morphology of the electrocatalysts and the fuel cell performance is elucidated. The most crucial preparation parameters for the optimization of the various features affecting the fuel cell performance of this promising class of ORR electrocatalysts are identified

    Interplay between structural and electrochemical properties of Pt-Rh carbon nitride electrocatalysts for the oxygen reduction reaction

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    This report describes a new family of bimetal carbon nitride (CN) electrocatalysts for the oxygen reduction reaction (ORR) for application in polymer electrolyte membrane fuel cells (PEMFCs). The materials, which bear active sites based on Pt and Rh, are prepared with a three-step protocol consisting of: (1) the synthesis of a homogeneous zeolitic inorganic–organic polymer electrolyte (Z-IOPE) precursor; (2) the pyrolysis of the precursor at a temperature Tf = 400, 500, 600, 700 or 900 ◦C; (3) the activation, yielding the final product. It is found that Tf has a major effect on the structure and the electrochemical properties of these electrocatalysts, as determined from a wide array of independent characterization techniques including: high-resolution thermogravimetry (HR-TGA); Fourier-transform medium infrared (FT-MIR), Fourier-transform far infrared (FT-FIR) and confocal micro-Raman spectroscopies; powder X-ray diffraction (powder XRD); X-ray photoelectron spectroscopy (XPS); and electrochemical investigations carried out with the cyclic voltammetry thin-film rotating disk electrode (CV-TF-RDE) method. All the information is integrated to propose a comprehensive model correlating the effect of Tf on the structure of the materials with the corresponding electrochemical performance. The best results in the ORR are obtained with materials prepared at 600 ≤ Tf ≤ 700 ◦C. These systems present the optimal compromise between the size of the metal-rich nanoparticles, the degree of graphitization of the carbon nitride support and the concentration of ligands blocking the active sites. The best Pt-Rh electrocatalysts exhibit an ORR activity very similar to the Pt/C reference. In addition, the peculiar structure of the proposed materials, which are characterized by active sites supported on the carbon nitride bulky materials, results in a better tolerance toward typical contaminants in the ORR process such as chloride anions with respect to the Pt/C reference. © 2011 Elsevier Ltd. All rights reserve

    Polyurethane-Based Electrostrictive Nanocomposites as High Strain-Low Frequency Mechanical Energy Harvesters

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    Harvesting of wasted mechanical energy is increasingly important for powering wearable electronics in Internet-of-Things world. Here, we report on innovative nanocomposites made of thermoplastic polyurethane (TPU) and a high-dielectric constant ceramic nano-filler (CaCu3Ti4O12), which offer good results in recovering energy by human gait. Power densities of the order of 300 W cm-3 at 12% strain were obtained with 50 vol% of filler. The film was strained more than 105 times without losing its properties. By means of careful broadband electric spectroscopy coupled with microstructure analysis, we were able to address the mechanisms underlying energy recovery. Our model allows optimal tailoring of electrostrictive nano-composite harvesters

    The social structure, ecology and pathogens of bats in the UK

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    This thesis examines the ecology, parasites and pathogens of three insectivorous bat species in Wytham Woods, Oxfordshire; Myotis nattereri (Natterer’s bat), M. daubentonii (Daubenton’s bat) and Plecotus auritus (Brown long-eared bat). The population structure was assessed by monitoring associations between ringed individuals, utilising recent advances in social network analysis. Populations of both M. daubentonii and M. nattereri were found to subdivide into tight-knit social groups roosting within small areas of a continuous woodland (average minimum roost home range of 0.23km2 and 0.17km2 respectively). If this population structure is a general attribute of these species it may make them more sensitive to small scale habitat change than previously thought and has implications for how diseases may spread through the population. M. daubentonii had a strong preference for roosts close to water, away from woodland edge and in areas with an easterly aspect. The factors driving roost choice in M. nattereri and P. auritus remain elusive. The segregation of M. daubentonii into bachelor and nursery colonies was not a result of the exclusion of males from roosts close to water by females, or variation in microclimate preferences between the sexes, as was predicted. Body condition (weight/forearm length) was correlated with host characteristics including age and reproductive status, and weather variables. Astroviruses and Coronaviruses, which have characteristics typical of zoonotic viruses, were identified in UK bat species for the first time. Coronaviruses identified formed species-specific clades while Astroviruses were highly diverse. Though not closely related to human viruses these are potential zoonotic diseases of the future. Models of Coronavirus and ectoparasite distribution suggest individual attributes (e.g. sex and age) and population structure (e.g. the formation of nursery and bachelor colonies) are important predictors of parasite and pathogen prevalence. This study characterises a system that offers many opportunities for future research including studies of sociality, disease modelling and conservation management.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

    Interplay between Composition, Structure, and Properties of New H3PO4-Doped PBI4N-HfO2 Nanocomposite Membranes for High-Temperature Proton Exchange Membrane Fuel Cells

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    Polybenzimidazole (PBI) has become a popular polymer of choice for the preparation of membranes for potential use in high-temperature proton exchange membrane polymer fuel cells. Phosphoric acid-doped composite membranes of poly[2,2′-(m-phenylene)-5,5′-bibenzimidazole] (PBI4N) impregnated with hafnium oxide nanofiller with varying content levels (0–18 wt %) have been prepared. The structure–property relationships of both the undoped and acid-doped composite membranes are studied using thermogravimetric analysis, modulated differential scanning calorimetry, dynamic mechanical analysis, wide-angle X-ray scattering, infrared spectroscopy, and broadband electrical spectroscopy. Results indicate that the presence of nanofiller improves the thermal and mechanical properties of the undoped membranes and facilitates a greater level of acid uptake. The degree of acid dissociation within the acid-doped membranes is found to increase with increasing nanofiller content. This results in a conductivity, at 215 °C and a nanofiller level x ≥ 0.04, of 9.0 × 10–2 S cm–1 for [PBI4N(HfO2)x](H3PO4)y. This renders nanocomposite membranes of this type as good candidates for use in high temperature proton exchange membrane fuel cells (HT-PEMFCs)
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