Exsolved nickel nanoparticles acting as oxygen storage reservoirs and active sites for redox CH4 conversion

The growing demand for H2 and syngas requires the development of new, more efficient processes and materials for their production, especially from CH4 that is a widely available resource. One process that has recently received increased attention is chemical looping CH4 partial oxidation, which, however, poses stringent requirements on material design, including fast oxygen exchange and high storage capacity, high reactivity toward CH4 activation, and resistance to carbon deposition, often only met by composite materials. Here we design a catalytically active material for this process, on the basis of exsolution from a porous titanate. The exsolved Ni particles act as both oxygen storage centers and as active sites for CH4 conversion under redox conditions. We control the extent of exsolution, particle size, and population of Ni particles in order to tune the oxygen capacity, reactivity, and stability of the system and, at the same time, obtain insights into parameters affecting and controlling exsolution

Low temperature methane conversion with perovskite-supported exo/endo-particles

Lowering the temperature at which CH4 is converted to useful products has been long-sought in energy conversion applications. Selective conversion to syngas is additionally desirable. Generally, most of the current CH4 activation processes operate at temperatures between 600 and 900 °C when non-noble metal systems are used. These temperatures can be even higher for redox processes where a gas phase–solid reaction must occur. Here we employ the endogenous-exsolution concept to create a perovskite oxide with surface and embedded metal nanoparticles able to activate methane at temperatures as low as 450 °C in a cyclic redox process. We achieve this by using a non-noble, Co–Ni-based system with tailored nano- and micro-structure. The materials designed and prepared in this study demonstrate long-term stability and resistance to deactivation mechanisms while still being selective when applied for chemical looping partial oxidation of methane

Low temperature methane conversion with perovskite-supported: exo / endo-particles

Lowering the temperature at which CH(4)is converted to useful products has been long-sought in energy conversion applications. Selective conversion to syngas is additionally desirable. Generally, most of the current CH(4)activation processes operate at temperatures between 600 and 900 degrees C when non-noble metal systems are used. These temperatures can be even higher for redox processes where a gas phase-solid reaction must occur. Here we employ the endogenous-exsolution concept to create a perovskite oxide with surface and embedded metal nanoparticles able to activate methane at temperatures as low as 450 degrees C in a cyclic redox process. We achieve this by using a non-noble, Co-Ni-based system with tailored nano- and micro-structure. The materials designed and prepared in this study demonstrate long-term stability and resistance to deactivation mechanisms while still being selective when applied for chemical looping partial oxidation of methane

Material migration and fuel retention studies during the JET carbon divertor campaigns

The first divertor was installed in the JET machine between 1992 and 1994 and was operated with carbon tiles and then beryllium tiles in 1994–5. Post-mortem studies after these first experiments demonstrated that most of the impurities deposited in the divertor originate in the main chamber, and that asymmetric deposition patterns generally favouring the inner divertor region result from drift in the scrape-off layer. A new monolithic divertor structure was installed in 1996 which produced heavy deposition at shadowed areas in the inner divertor corner, which is where the majority of the tritium was trapped by co-deposition during the deuterium-tritium experiment in 1997. Different divertor geometries have been tested since such as the Gas-Box and High-Delta divertors; a principle objective has been to predict plasma behaviour, transport and tritium retention in ITER. Transport modelling experiments were carried out at the end of four campaigns by puffing 13C-labelled methane, and a range of diagnostics such as quartz-microbalance and rotating collectors have been installed to add time resolution to the post-mortem analyses. The study of material migration after D-D and D-T campaigns clearly revealed important consequences of fuel retention in the presence of carbon walls. They gave a strong impulse to make a fundamental change of wall materials. In 2010 the carbon divertor and wall tiles were removed and replaced with tiles with Be or W surfaces for the ITER-Like Wall Project

Endogenous nanoparticles strain perovskite host lattice providing oxygen capacity and driving oxygen exchange and CH4 conversion to syngas

Particles dispersed on the surface of oxide supports have enabled a wealth of applications in electrocatalysis, photocatalysis, and heterogeneous catalysis. Dispersing nanoparticles within the bulk of oxides is, however, synthetically much more challenging and therefore less explored, but could open new dimensions to control material properties analogous to substitutional doping of ions in crystal lattices. Here we demonstrate such a concept allowing extensive, controlled growth of metallic nanoparticles, at nanoscale proximity, within a perovskite oxide lattice as well as on its surface. By employing operando techniques, we show that in the emergent nanostructure, the endogenous nanoparticles and the perovskite lattice become reciprocally strained and seamlessly connected, enabling enhanced oxygen exchange. Additionally, even deeply embedded nanoparticles can reversibly exchange oxygen with a methane stream, driving its redox conversion to syngas with remarkable selectivity and long term cyclability while surface particles are present. These results not only exemplify the means to create extensive, self-strained nanoarchitectures with enhanced oxygen transport and storage capabilities, but also demonstrate that deeply submerged, redox-active nanoparticles could be entirely accessible to reaction environments, driving redox transformations and thus offering intriguing new alternatives to design materials underpinning several energy conversion technologies

Dielectric Barrier Plasma Discharge Exsolution of Nanoparticles at Room Temperature and Atmospheric Pressure

Exsolution of metal nanoparticles (NPs) on perovskite oxides has been demonstrated as a reliable strategy for producing catalyst‐support systems. Conventional exsolution requires high temperatures for long periods of time, limiting the selection of support materials. Plasma direct exsolution is reported at room temperature and atmospheric pressure of Ni NPs from a model A‐site deficient perovskite oxide (La0.43Ca0.37Ni0.06Ti0.94O2.955). Plasma exsolution is carried out within minutes (up to 15 min) using a dielectric barrier discharge configuration both with He‐only gas as well as with He/H2 gas mixtures, yielding small NPs

Dielectric barrier plasma discharge exsolution of nanoparticles at room temperature and atmospheric pressure

Funding: his work was supported by EPSRC through the UK Catalysis Hub (EP/R027129/1) and the Emergent Nanomaterials-Critical Mass Initiative (EP/R023638/1, EP/R023921/1, EP/R023522/1, EP/R008841/1) as well as the Royal Society (IES∖R2∖212049). F.F. gratefully acknowledges support from the National Research Council of Italy (2020 STM program). I.S.M. acknowledges funding from the Royal Academy of Engineering through a Chair in Emerging Technologies Award entitled “Engineering Chemical Reactor Technologies for a Low-Carbon Energy Future” (Grant CiET1819∖2∖57). K.K. acknowledges funding from the Henry Royce Institute (EP/X527257/1), Royal Society (RGS∖R2∖222062), and EPSRC (EP/Y015487/1).Exsolution of metal nanoparticles (NPs) on perovskite oxides has been demonstrated as a reliable strategy for producing catalyst-support systems. Conventional exsolution requires high temperatures for long periods of time, limiting the selection of support materials. Plasma direct exsolution is reported at room temperature and atmospheric pressure of Ni NPs from a model A-site deficient perovskite oxide (La0.43Ca0.37Ni0.06Ti0.94O2.955). Plasma exsolution is carried out within minutes (up to 15 min) using a dielectric barrier discharge configuration both with He-only gas as well as with He/H2 gas mixtures, yielding small NPs (<30 nm diameter). To prove the practical utility of exsolved NPs, various experiments aimed at assessing their catalytic performance for methanation from synthesis gas, CO, and CH4 oxidation are carried out. Low-temperature and atmospheric pressure plasma exsolution are successfully demonstrated and suggest that this approach could contribute to the practical deployment of exsolution-based stable catalyst systems.Peer reviewe

Dielectric Barrier Plasma Discharge Exsolution of Nanoparticles at Room Temperature and Atmospheric Pressure

Exsolution of metal nanoparticles (NPs) on perovskite oxides has beendemonstrated as a reliable strategy for producing catalyst-support systems.Conventional exsolution requires high temperatures for long periods of time,limiting the selection of support materials. Plasma direct exsolution isreported at room temperature and atmospheric pressure of Ni NPs from amodel A-site deficient perovskite oxide (La 0.43 Ca 0.37 Ni 0.06 Ti 0.94 O2.955 ). Plasmaexsolution is carried out within minutes (up to 15 min) using a dielectricbarrier discharge configuration both with He-only gas as well as with He/H2gas mixtures, yielding small NPs (&lt;30 nm diameter). To prove the practicalutility of exsolved NPs, various experiments aimed at assessing their catalyticperformance for methanation from synthesis gas, CO, and CH4 oxidation arecarried out. Low-temperature and atmospheric pressure plasma exsolution aresuccessfully demonstrated and suggest that this approach could contribute tothe practical deployment of exsolution-based stable catalyst systems

Rare coding SNP in DZIP1 gene associated with late-onset sporadic Parkinson's disease

We present the first application of the hypothesis-rich mathematical theory to genome-wide association data. The Hamza et al. late-onset sporadic Parkinson's disease genome-wide association study dataset was analyzed. We found a rare, coding, non-synonymous SNP variant in the gene DZIP1 that confers increased susceptibility to Parkinson's disease. The association of DZIP1 with Parkinson's disease is consistent with a Parkinson's disease stem-cell ageing theory.Comment: 14 page

Cerebrospinal Fluid Concentration of Brain-Derived Neurotrophic Factor and Cognitive Function in Non-Demented Subjects

Brain-derived neurotrophic factor (BDNF) is an activity-dependent secreted protein that is critical to organization of neuronal networks and synaptic plasticity, especially in the hippocampus. We tested hypothesis that reduced CSF BDNF is associated with age-related cognitive decline.CSF concentration of BDNF, Abeta(42) and total tau were measured in 128 cognitively normal adults (Normals), 21 patients with Alzheimer's disease (AD), and nine patients with Mild Cognitive Impairment. Apolipoprotein E and BDNF SNP rs6265 genotype were determined. Neuropsychological tests were performed at baseline for all subjects and at follow-up visits in 50 Normals. CSF BDNF level was lower in AD patients compared to age-matched Normals (p = 0.02). CSF BDNF concentration decreased with age among Normals and was higher in women than men (both p<0.001). After adjusting for age, gender, education, CSF Abeta(42) and total tau, and APOE and BDNF genotypes, lower CSF BDNF concentration was associated poorer immediate and delayed recall at baseline (both p<0.05) and in follow up of approximately 3 years duration (both p<0.01).Reduced CSF BDNF was associated with age-related cognitive decline, suggesting a potential mechanism that may contribute in part to cognitive decline in older individuals