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Composite materials consisting of metal and metal oxide phases are being researched intensively for various energy conversion applications where they are often expected to operate under redox conditions at elevated temperature. Understanding of the dynamics of composite evolution during redox cycling is still very limited, yet critical to maximising performance and increasing durability. Here we track the microstructural evolution of a single composite particle over 200 redox cycles for hydrogen production by chemical looping, using multi-length scale X-ray computed tomography. We show that redox cycling triggers a centrifugal redispersion of the metal phase and a centripetal clustering of porosity, both seemingly driven by the asymmetric nature of oxygen exchange in composites. Initially, the particle develops a large amount of internal porosity which boosts activity, but on the long term this facilitates structural and compositional reorganisation and eventually degradation. These results provide valuable insight into redox-driven microstructural changes and also for the design of new composite materials with enhanced durability. [ABSTRACT FROM AUTHOR]

The Mariana Trough, a relatively simple intra-oceanic back-arc basin, is ideal for investigating magmatic processes and mantle-crust interaction in a subduction setting. We present new major- and trace element compositions for 31 basaltic lava and glass samples from the Mariana Trough back-arc spreading center. The studied lavas include phenocrysts of plagioclase, olivine and pyroxene. Major element compositions show that these lavas range from tholeiitic basalt to basaltic andesite, and belong to a sub-alkali tholeiitic series produced by fluid-influenced fractional crystallization of primary basaltic melts. Trace element compositions show that these lavas are transitional between typical normal mid-ocean ridge basalts (MORB) and island arc basalt (IAB), and are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs). Trace element ratios, e.g., Ba/Th, Pb/Ce, Th/Nd, La/Sm, Th/Nb, Ba/Nb and Th/Nb, indicate that the mantle from which these lavas were derived underwent modification resulting from the addition of multiple subduction components. Some typical trace element ratios (e.g., Ba/Nb- total subduction component, Ba/Th- shallow subduction, and Th/Nb-deep subduction component) from our new data and the literature suggest that a latitudinal variation exists in addition to subduction components, and indicates a more complex and heterogeneous distribution of subduction components in the Mariana back-arc region. We suggest that, (1) compared to back-arc locations at 18° N and 15.5° N, lavas from back-arc locations at 17° N indicate higher levels of modification by hydrous fluid released from the subducted slab, and (2) compared to back-arc locations at 17° N and 15.5° N, petrogenesis of lavas from back-arc locations at 18° N indicates a greater influence of sediment melt. [ABSTRACT FROM AUTHOR]

Metallic nanoparticles exsolved at the surface of perovskite oxides have been recently shown to unlock superior catalytic activity and durability towards various chemical reactions of practical importance. For example, for the CO oxidation reaction, exsolved Ni nanoparticles in oxidised form exhibit site activities approaching those of noble metals. This is of particular interest for the prospect of replacing noble metals with earth-abundant metal/metal oxide catalysts in the automotive exhaust control industry. Here we show that for the CO oxidation reaction, the functionality of exsolved Ni nanoparticles can be further improved when Fe is co-exsolved with Ni, as Fe–Ni alloy nanoparticles, eventually forming mixed oxide nanoparticles. As compared to the Ni nanoparticles, the alloy nanoparticles exhibit higher site activities, greatly improved durability over 170 h of continuous testing and increased tolerance towards sulphur-based atmospheres. Similarly to the single metal nanoparticles, the alloys demonstrate outstanding microstructural stability and high tolerance towards coking. These results open additional directions for tailoring the activity and durability of exsolved materials for the CO oxidation reaction and beyond. [ABSTRACT FROM AUTHOR]

Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity. [ABSTRACT FROM AUTHOR]

A comparative study between a classic and a wireless electrochemical promotion experiment was undertaken as a tool towards the better understanding of both systems. The catalytic modification of a platinum catalyst for ethylene oxidation was studied. The catalyst was supported on yttria-stabilised-zirconia (YSZ), a known pure oxide ion conductor, for the classic experiment and La0.6Sr0.4Co0.2Fe0.8O3–δ—a mixed oxide ion electronic conductor—was used for the wireless experiment. The two systems showed certain similarities in terms of the reaction classification (in both cases electrophobic behaviour was observed) and the promotion mechanism. Significant difference was observed in the time scales and the reversibility of the induced rate modification. [ABSTRACT FROM AUTHOR]

The wet air oxidation (WAO) and ultrasound irradiation of sodium dodecylbenzene sulfonate in water was investigated. Heterogeneous catalysts such as a mixed copper-zinc oxide and noble metals, namely platinum, palladium and ruthenium, generally improved the efficiency of the respective uncatalysed process. The performance of sonochemical treatment, although less effective than WAO at high organic concentrations, may improve by a Fenton-like reaction mechanism on the addition of ferrous ions. [ABSTRACT FROM AUTHOR]

Integrated study of rock assemblage, tectonic setting, geochemical feature, fossil contained and isotopic geochronology on the metamorphic mixed bodies, exposed in the Jinshajiang suture zone, suggests that one informal lithostratigraphic unit, the Eaqing Complex, and three tectono-stratigraphic units, the Jinshajiang ophiolitic melange, the Gajinxueshan Group and the Zhongxinrong Group, can be recognized there. It is first pointed out that the redefined Eaqing Complex might represent the Meso- to Neo-Proterozoic remnant metamorphic basement or mi-crocontinental fragment in the Jinshajiang area. The original rocks of it should be older than (1627 ±192) Ma based on the geochronological study. The zircon U-Pb age of plagiogranites within the Jinshajiang ophiolitic assemblage is dated for the first time at (294 ± 3) Ma and (340 ± 3) Ma respectively. The Jinshajiang ophiolite is approximately equivalent to the Ailaoshan ophiolite in the formation age, covering the interval from the Late Devonian to the Carboniferous. Dating of U-Pb age from basalt interbeds indicates that the redefined Gajinxueshan Group and Zhongxinrong Group may be considered Carboniferous to Permian and latest Permian to Middle Triassic in age. In geotectonic terms the Jinshajiang suture zone is thought to be a back-arc basin in the eastern margin of the Paleo-Tethys. This back-arc basin started in the Late Devonian, and formed in the Devonian-Carboniferous. The collision event around the Permian/Triassic boundary to the Middle Triassic led to the closure of the back-arc basin and formation of suture. [ABSTRACT FROM AUTHOR]