In situ XAFS of acid-resilient iridate pyrochlore oxygen evolution electrocatalysts under operating conditions.

Pyrochlore iridates (Na,Ca)2-xIr2O6·H2O are acid-stable electrocatalysts that are candidates for use in electrolysers and fuel cells. Ir LIII-edge X-ray absorption fine structure spectroscopy in 1 M H2SO4 at oxygen evolution conditions suggests the involvement of the electrons from the conduction band of the metallic particles, rather than just surface iridium reacting.

Hydrothermal Synthesis of Iridium-Substituted NaTaO3 Perovskites.

Iridium-containing NaTaO3 is produced using a one-step hydrothermal crystallisation from Ta2O5 and IrCl3 in an aqueous solution of 10 M NaOH in 40 vol% H2O2 heated at 240 °C. Although a nominal replacement of 50% of Ta by Ir was attempted, the amount of Ir included in the perovskite oxide was only up to 15 mol%. The materials are formed as crystalline powders comprising cube-shaped crystallites around 100 nm in edge length, as seen by scanning transmission electron microscopy. Energy dispersive X-ray mapping shows an even dispersion of Ir through the crystallites. Profile fitting of powder X-ray diffraction (XRD) shows expanded unit cell volumes (orthorhombic space group Pbnm) compared to the parent NaTaO3, while XANES spectroscopy at the Ir LIII-edge reveals that the highest Ir-content materials contain Ir4+. The inclusion of Ir4+ into the perovskite by replacement of Ta5+ implies the presence of charge-balancing defects and upon heat treatment the iridium is extruded from the perovskite at around 600 °C in air, with the presence of metallic iridium seen by in situ powder XRD. The highest Ir-content material was loaded with Pt and examined for photocatalytic evolution of H2 from aqueous methanol. Compared to the parent NaTaO3, the Ir-substituted material shows a more than ten-fold enhancement of hydrogen yield with a significant proportion ascribed to visible light absorption.

A hydrothermally stable ytterbium metal-organic framework as a bifunctional solid-acid catalyst for glucose conversion.

Yb6(BDC)7(OH)4(H2O)4 contains both bridging hydroxyls and metal-coordinated waters, possessing Brønsted and Lewis acid sites. The material crystallises from water at 200 °C. Using the solid as a heterogenous catalyst, glucose is converted into 5-hydroxymethylfurfural, via fructose, with a total selectivity of ∼70% after 24 hours at 140 °C in water alone: the material is recyclable with no loss of crystallinity.

Exceptionally Efficient and Recyclable Heterogeneous Metal-Organic Framework Catalyst for Glucose Isomerization in Water.

Heterogeneous catalysts are desired for the conversion of glucose, the most abundant sugar in renewable biomass, but presently their synthesis requires highly toxic chemicals with long synthesis times. We report the conversion of glucose into fructose and 5-hydroxymethylfurfural on a heterogeneous catalyst that is stable and selective and operates in the most environmentally benign solvent, water. We used a bifunctional solid with Lewis and Brønsted acid sites by partially replacing the organic linker of the zirconium organic framework UiO-66 with 2-monosulfo-benzene-1,4-dicarboxylate. This catalyst showed high product selectivity (90 %) to 5-hydroxymethylfurfural and fructose at 140 °C in water after a reaction time of 3 h. It was recyclable and showed only a minor loss in activity after the third recycle, offering a realistic solution for the bottleneck glucose isomerization reaction for scale-up and industrial application of biomass utilization.

Prevalence of white matter hyperintensities in a young healthy population.

BACKGROUND AND PURPOSE: White matter hyperintensities (WMHs) are bright objects observed in the white matter on brain magnetic resonance (MR) imaging. WMHs are often reported as "normal" findings but may represent pathological changes. The prevalence of WMHs appears to increase with increasing age although both the typical timing and clinical significance of their appearance among medically and neurologically healthy persons remains unclear. We assessed the prevalence of WMHs in a cohort of younger healthy subjects. METHODS: Our study comprised 243 healthy subjects ages 16-65 years from our prospective normative MR imaging database. MR scans were rated for presence of periventricular and centrum semiovale WMHs using a four-point visual semi-quantitative scale. RESULTS: WMHs occurred in 5.3% (13 of 243) of subjects. All WMHs were small (rating of 0.5) except one subject age 65 years who had large WMHs (ratings of 2). The median age for subjects with no WMHs was 34.5 years compared to 57.0 years for subjects with WMHs. There were no gender differences (P= .76). Older age correlated with presence of WMHs (r = 0.24; P= .01). Age greater than 55 years had a 10-fold increase in the prevalence of WMHs compared to age < or =55 years (odds ratio = 10.01; 95% confidence interval = 3.1-32.3; P < .001). CONCLUSION: WMHs were uncommon in a younger healthy population screened for comorbid diseases, but increased 10-fold in subjects over 55 years of age. When present, the WMHs are generally small (rating of 0.5). While large WMHs appear to be associated with cognitive deterioration, the optimum threshold for identification, clinical significance, and prognostic value of smaller white matter changes requires further research.