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Abstract: Cobalt is essential for the modern technology that underpins the decarbonisation of our economies, but its supply is limited leading to its designation as a critical metal. Cobalt biogeochemistry is poorly understood, yet knowledge of how biogeochemical cycling impacts cobalt behaviour could assist the development of new techniques to recover cobalt from ores, and so improve the security of supply. Laterites are an important source of cobalt, they are primarily processed for nickel using energy or chemical intensive processes, with cobalt recovered as a by-product. Metal-reducing conditions were stimulated in laterite sediment microcosms by the addition of simple and cheaply available organic substrates (acetate or glucose). At the end of the experiment the amount of easily recoverable cobalt (aqueous or extractable with acetic acid) increased from < 1 % to up to 64 %, which closely mirrored the behaviour of manganese, while only a small proportion of iron was transformed into an easily recoverable phase. Sequencing of the microbial community showed that the addition of organic substrates stimulated the growth of indigenous prokaryotes closely related to known manganese(IV)/iron(III)-reducers, particularly from the Clostridiales, and that fungi assigned to Penicillium, known to produce organic acids beneficial for leaching cobalt and nickel from laterites, were identified. Overall, the results indicate that the environmental behaviour of cobalt in laterites is likely to be controlled by manganese biogeochemical cycling by microorganisms. These results are compelling given that similar behaviour was observed in four laterites (Acoje, Çaldağ, Piauí and Shevchenko) from different continents. A new bioprocessing strategy is proposed whereby laterites are treated with an organic substrate to generate metal-reducing conditions, then rinsed with acetic acid to remove the cobalt. Not only are organic substrates environmentally-friendly and potentially sourced from waste carbon substrates, a minimal amount of iron oxides was mobilised and consequently less waste generated.

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Abstract: The catalytic activities of supported metal nanoparticles can be tuned by appropriate design of synthesis strategies. Each step in a catalyst synthesis method can play an important role in preparing the most efficient catalyst. Here we report the careful manipulation of the post-synthetic heat treatment procedure—together with control over the metal loading—to prepare a highly efficient 0.2 wt% Pt/TiO2 catalyst for the chemoselective hydrogenation of 3-nitrostyrene. For Pt/TiO2 catalysts with 0.2 and 0.5 wt% loading levels, reduction at 450 °C induces the coverage of TiOx over Pt nanoparticles through a strong metal–support interaction, which is detrimental to their catalytic activities. However, this can be avoided by following calcination treatment with reduction (both at 450 °C), allowing us to prepare an exceptionally active catalyst. Detailed characterization has revealed that the peripheral sites at the Pt/TiO2 interface are the most likely active sites for this hydrogenation reaction.

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Abstract: We present the synthesis of metal nanowires in a multiplexed device configuration using single‐walled carbon nanotubes (SWNTs) as nanoscale vector templates. The SWNT templates control the dimensionality of the wires, allowing precise control of their size, shape, and orientation; moreover, a solution‐processable approach enables their linear deposition between specific electrode pairs in electronic devices. Electrical characterization demonstrated the successful fabrication of metal nanowire electronic devices, while multiscale characterization of the different fabrication steps revealed details of the structure and charge transfer between the material encapsulated and the carbon nanotube. Overall the strategy presented allows facile, low‐cost, and direct synthesis of multiplexed metal nanowire devices for nanoelectronic applications.

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Abstract: A legacy of radioactive waste has accumulated since the late 1940s and safe containment of long lived, highly radioactive waste is crucial for the future of nuclear power. A geological disposal facility (GDF) is the preferred method for the safe disposal of radioactive wastes; a multifaceted approach, using both engineered and natural barriers, to maximise the time between the breakdown of barriers and the final interaction with the environment and subsequently people. Clay is likely form an integral part of the engineered barrier system (EBS) surrounding the waste canisters in many proposed GDFs for heat generating radioactive wastes. The clay selected for this purpose would need to have the necessary physical and chemical properties to protect the waste container against corrosion and also to limit the release of radionuclides from the waste after container failure. Clays have a number of advantageous properties, such as high sorption capacity for radionuclides, small pore structure restricting microbial activity, and stability over geological time scales. Substitution of cations (Fe2+/3+, Mg2+, Al3+) into octahedral and tetrahedral (Al3+ and Si4+) sheets give a net negative charge on the clay layers giving interlayer spaces in-between; hydrated cations balance the negative charge within the interlayer space and cause the clay to swell filling surrounding gaps/cracks, avoiding advective flow, stabilizing the canister, and making diffusion the predominant transport mechanism within the barrier. A number of challenges such as heat (from the high level wastes 160 °C), with small changes being resisted further by divalent interlayer cations. gamma irradiation was shown to generate charge defects within the clay, increasing surface potential and activating redox properties (Fe); alpha irradiation showed localised amorphisation of the clay structure with long range order maintained. Maximising the ability of the clay barrier to withstand the challenges expected in the GDF environment would allow for the strengthening of public opinion and a faster, smaller (footprint), cheaper and safer GDF for high level, heat generating, radioactive wastes to be produced.

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Abstract: Uranium (U) contamination of ground and surface waters poses an acute hazard on the ecosystem and human health. Since the discovery of microbial U(VI) reduction, U bioremediation has been explored as a promising and cost-effective method compared to traditional treatments. The speciation of the bioreduction product was originally stated to be uraninite (UO2) which is a recalcitrance crystalline U(IV) species. On the other hand, recent studies demonstrated that non-crystalline species (NCU4) are the dominant product of bioreduction. Since NCU4 species are more labile than UO2, new concerns are associated with the long-term stability of these U(IV) products. In fact, the effectiveness of bioremediation depends on the resistance of NCU4 species to oxidation and remobilization into solution. In this regard, it was previously hypothesized that aging might transform NCU4 to UO2 that would enhance the resistance of U(IV) to oxidation and release into the aqueous phase. We investigated this hypothesis by incubating NCU4 species immobilized in natural sediments under anoxic conditions for a period of 12 months. We systematically probe the speciation of U in the sediment using X-ray absorption spectroscopy. Under the investigated conditions, NCU4 does not age to UO2. Thus it is likely that NCU4 produced during bioremediation persists in the subsurface even for an extended period of time if anoxia is maintained. Therefore the re-mediated site remains vulnerable to events that bring oxygen into the reduced zone. In fact, NCU4 species are rapidly oxidized upon exposure to oxygen. Furthermore, we demonstrated that under certain conditions (i.e., high dissolved oxygen (DO) concentration), the presence of FeS accelerates the oxidation and re-mobilization of NCU4 via the production of reactive oxygen species. Since ROS production during FeS oxidation depends on the concentration of DO and the speciation of Fe(II) in the sediments, at low DO concentrations, low amounts of ROS were detected, and the enhancement of U(IV) oxidation by FeS be-came negligible. Moreover, this thesis investigates the isotopic fractionation (238U/235U) during abiotic reduction by magnetite (Fe3O4), a Fe(II) bearing mineral capable of reducing U(VI) that is commonly found in bioreduced zones. The results of preliminary experiments confirmed that U reduction by Fe3O4 has opposite fractionation than predicted by the nuclear field shift effect suggesting that a kinetic effect may drive fractionation during reduction. Preliminary XAS speciation of U immobilized on the surface of magnetite report that U(V) may occurs during reduction.