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Abstract: The emerging field of lead-based hybrid organic-inorganic perovskite (HOIP) photovoltaic devices has attracted a great deal of attention due to their very high conversion efficiencies and straightforward fabrication methods. Unfortunately a major obstacle to commercialization remains the high toxicity of lead. Whilst to date the focus has been on understanding and improving device performance, there has been no reported effort to develop methods to recover and recycle the lead from these materials. In this work we demonstrate a simple, low-cost and environmentally friendly method of recycling lead from HOIP photovoltaics by dissolution and selective electrodeposition using a deep eutectic solvent. We demonstrate that up to 99.8% of the lead is removed from the solvent. The results presented here provide a viable solution to lead-based HOIP photovoltaic recycling, and also open the possibility for providing an alternative method to conventional smelting in the recovery and recycling of different lead-based energy materials.

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Abstract: We report a microfocus X-ray absorption (XAS) investigation of a thin film sample from an iron contaminated wooden arrow tip raised from the seabed with the Mary Rose. The XAS studies were combined with optical and scanning electron microscopy measurements. The arrow tip had been treated with polyethylene glycol (PEG) soon after it had been raised and stored in a controlled environment. The measurements revealed a significant concentration of iron sulfide nanoparticles. This indicates that in this sample there was a reduction of the oxidative effects of the normal ambient atmosphere that is usually seen in untreated timbers. The film was treated overnight with an aqueous solution of diethylenetriaminepentaacetic acid (DTPA), which is normally very effective in sequestering iron. This had little effect in terms of removing iron from the film and possible explanations are discussed.

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Abstract: A modified hydrothermal synthesis, avoiding high temperature calcination, is used to produce nano-particulate rhodium doped strontium titanate in a single-step, maintaining the rhodium in the photocatalytically active +3 oxidation state as shown by X-ray spectroscopy. The photoactivity of the material is demonstrated through the decomposition of aqueous methyl orange and the killing of Escherichia coli in aqueous suspension, both under visible light activation. A sample of SrTiO3 containing 5 at% Rh completely decomposed a solution of methyl orange in less than 40 minutes and E. coli is deactivated within 6 hours under visible light irradiation.

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Abstract: Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF2, by ball milling it with BaF2, to create nanostructured Ba1-xCaxF2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including ‘simulating synthesis’, we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include: structural disorder, excess volume, pseudo vacancy arrays and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba1-xCaxF2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [Nature 2015, 512, 303] remarks that ‘classical crystallography is inadequate to describe systems with correlated disorder, but that geometric frustration has clear crystallographic signatures’. Here, we identify two possible crystallographic signatures: excess volume and correlated ‘snake-like’ ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013, 138, 12A538]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, branching of the ‘snake’ arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous or liquid states, and processes such as ionic conductivity, melting and crystallization.

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Abstract: The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds to have promise as a new class of high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion charge compensated by the transition-metal ions. The additional capacity is provided through charge compensation by oxygen-redox chemistry and some oxygen loss. It has been reported previously that O-redox occurs in O-2p orbitals that interact with alkali-ions in the transition-metal and alkali-ion layers (i.e. O-redox occurs in compounds containing Li+ - O2p - Li+ interactions). Na2/3[Mg0.28Mn0.72]O2 exhibits excess capacity; here we show this is also due to O-redox, despite Mg2+ residing in the transition-metal (TM) layers rather than alkali-metal ions, demonstrating that excess alkali-metal ions are not required to activate O-redox. We also show that unlike the alkali-rich compounds, Na2/3[Mg0.28Mn0.72]O2 does not lose O. Extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen promoting oxygen loss, whereas Mg2+ remains in Na2/3[Mg0.28Mn0.72]O2 stabilising oxygen.