Oxygen Hole Character and Lateral Homogeneity in PrNiO2+δ Thin Films

Using x-ray absorption spectroscopy with lateral resolution from the submillimeter to submicrometer range, we investigate the homogeneity, the chemical composition, and the nickel 3d- oxygen 2p charge transfer in topotactically reduced epitaxial PrNiO2+δ thin films. To this end, we use x-ray absorption spectroscopy in a standard experimental setup and in a soft x-ray microscope to probe the element and spatially resolved electronic structure modifications through changes of the nickel-2p and oxygen-1s absorption spectrum upon soft-chemistry reduction. We find that the reduction process is laterally homogeneous across a partially reduced PrNiO2+δ thin film sample for length scales down to 50 nm.

Unusual Luminescence of Quartz from La Sassa, Tuscany: Insights on the Crystal and Defect Nanostructure of Quartz

Quartz from La Sassa (Tuscany, Italy) presents a unique luminescence related to intrinsic and extrinsic defects in the crystal lattice due to the growth mechanisms in hydrothermal conditions. The bright fluorescence under the UV lamp was apparent to collectors since the early 1970s, and it entered the literature as a reference case of yellow-luminescent quartz. Early reports present the history of the discovery, the geological context, and preliminary luminescence measurements of the quartz nodules, suggesting various activators as potentially responsible of the peculiar luminescence effects: uranyl groups (UO22+), rare earths (Tb3+, Eu3+, Dy3+, Sm3+, Ce3+) and polycyclic aromatic compounds (PAH). Here, we report a full investigation of the La Sassa material, by a multi-analytical approach encompassing cathodoluminescence optical microscopy (OM-CL), laser-induced fluorescence (LIF), wavelength resolved thermally stimulated luminescence (WR-TSL), trace elements analysis by mass spectrometry (ICP-MS) and Raman spectroscopy (RS). The results provide a significant step forward in the interpretation of the luminescence mechanisms: the main luminescent centres are identified as alkali-compensated (mainly Li+ and Na+, K+ and H+) aluminum [AlO4/M+]0 centres substituting for Si, where the recombination of a self-trapped exciton (STE) or an electron at a nonbridging oxygen hole centre (NBOHC) are active.

Structural and Optical Modifications in the BaO-ZnO-LiF-B2O3-Yb2O3 Glass System after γ-Irradiation

A Yb3+-doped borate glass system was examined for the structural and optical modifications after γ-irradiation. Among the studied 10BaO-20ZnO-20LiF-(50-x)B2O3-xYb2O3 (x = 0.1, 0.5, 0.7, and 1.0 mol%) glasses, the 10BaO-20ZnO-20LiF-49.9B2O3-0.1Yb2O3 glass showed the highest thermoluminescence intensity, trap density, and trap depth. The glass was irradiated with the optimum γ-dose of 1 kGy towards the analysis of radiation-induced defects. The amorphous nature was preserved before and after irradiation. The glass density slightly increased after irradiation. The structural rearrangement was evident from the Fourier transform infrared spectroscopy by the appearance and disappearance of some bonds after γ-irradiation. The transformation of [BO4] units into [BO3] units and non-bridging oxygens was deduced. The color of the glass darkened after irradiation and the optical absorption intensity enhanced between 250 and 700 nm. The optical bandgap reduced and Urbach energy increased upon γ-dose exposure. The electron spin resonance of the irradiated glass exhibited two signals at g = 2.0167 and g = 1.9938, corresponding to the non-bridging oxygen hole center and Boron E’-center, respectively.

Radiation Effects on Pure-Silica Multimode Optical Fibers in the Visible and Near-Infrared Domains: Influence of OH Groups

Signal transmission over optical fibers in the ultraviolet to near-infrared domains remains very challenging due to their high intrinsic losses. In radiation-rich environments, this is made even more difficult due to the radiation-induced attenuation (RIA) phenomenon. We investigated here how the number of hydroxyl groups (OH) present in multi-mode (MM) pure-silica core (PSC) optical fibers influences the RIA levels and kinetics. For this, we tested three different fiber samples: one “wet”, one “dry” and one with an intermediate “medium” OH content. The RIA of the three samples was measured in the 400–900 nm (~3 eV to ~1.4 eV) spectral range during and after an X-ray irradiation at a dose rate of 6 Gy(SiO2) s−1 up to a total accumulated dose of 300 kGy(SiO2). Furthermore, we evaluated the H2-pre-loading efficiency in the medium OH sample to permanently improve both its intrinsic losses and radiation response in the visible domain. Finally, the spectral decomposition of the various RIA responses allows us to better understand the basic mechanisms related to the point defects causing the excess of optical losses. Particularly, it reveals the relationship between the initial OH groups content and the generation of non-bridging oxygen hole centers (NBOHCs). Moreover, the presence of hydroxyl groups also affects the contribution from other intrinsic defects such as the self-trapped holes (STHs) to the RIA in this spectral domain.

Coulombically-stabilized oxygen hole polarons enable fully reversible oxygen redox

Stabilizing high-valent redox couples and exotic electronic states necessitate an understanding of the stabilization mechanism. In oxides, whether they are being considered for energy storage or computing, highly oxidized oxide-anion...

Mutation of an atypical oxirane oxyanion hole improves regioselectivity of the α/β-fold epoxide hydrolase Alp1U.

Epoxide hydrolases (EHs) have been characterized and engineered as biocatalysts that convert epoxides to valuable chiral vicinal diol precursors of drugs and bioactive compounds. Nonetheless, the regioselectivity control of the epoxide ring opening by EHs remains challenging. Alp1U is an α/β-fold EH that exhibits poor regioselectivity in the epoxide hydrolysis of fluostatin C (1), and produces a pair of stereoisomers. Herein, we established the absolute configuration of the two stereoisomeric products and determined the crystal structure of Alp1U. A W186/W187/Y247 oxirane oxygen hole was identified in Alp1U that replaced the canonical Tyr/Tyr pair in α/β-EHs. Mutation of residues in the atypical oxirane oxygen hole of Alp1U improved the regioselectivity for epoxide hydrolysis on 1. The single site Y247F mutation led to highly regioselective (98%) attack at C-3 of 1, while the double mutation W187F/Y247F resulted in regioselective (94%) nucleophilic attack at C-2. Furthermore, single crystal X-ray structures of the two regioselective Alp1U variants in complex with 1 were determined. These findings allowed insights into the reaction details of Alp1U, and provided a new approach for engineering regioselective epoxide hydrolases.

Defects in nanosilica catalytically convert CO2to methane without any metal and ligand

Active and stable metal-free heterogeneous catalysts for CO2fixation are required to reduce the current high level of carbon dioxide in the atmosphere, which is driving climate change. In this work, we show that defects in nanosilica (E′ centers, oxygen vacancies, and nonbridging oxygen hole centers) convert CO2to methane with excellent productivity and selectivity. Neither metal nor complex organic ligands were required, and the defect alone acted as catalytic sites for carbon dioxide activation and hydrogen dissociation and their cooperative action converted CO2to methane. Unlike metal catalysts, which become deactivated with time, the defect-containing nanosilica showed significantly better stability. Notably, the catalyst can be regenerated by simple heating in the air without the need for hydrogen gas. Surprisingly, the catalytic activity for methane production increased significantly after every regeneration cycle, reaching more than double the methane production rate after eight regeneration cycles. This activated catalyst remained stable for more than 200 h. Detailed understanding of the role of the various defect sites in terms of their concentrations and proximities as well as their cooperativity in activating CO2and dissociating hydrogen to produce methane was achieved.

Deciphering Silicification Pathways of Fossil Forests: Case Studies from the Late Paleozoic of Central Europe

The occurrence and formation of silicified wood from five late Paleozoic basins in Central Europe was investigated. Fossil wood from diverse geological settings was studied using field observations, taphonomic determinations as well as mineralogical analyses (polarizing microscopy, cathodoluminescence (CL) microscopy and spectroscopy). The results indicate that silicification is either a monophase or multiphase process under varying physico-chemical conditions. In particular, CL studies revealed complex processes of silica accumulation and crystallization. The CL characteristics of quartz phases in silicified wood can mostly be related to blue (390 and 440 nm), yellow (580 nm), and red (650 nm) emission bands, which may appear in different combinations and varying intensity ratios. Yellow CL is typical for initial silicification, reflecting quick precipitation under oxygen-deficient conditions caused by initial decay of the organic material. Blue CL is predominantly of secondary origin, resulting from replacement of precursor phases by a secondary hydrothermal quartz generation or subsequent silicification of wood. The red CL can be related to a lattice defect (non-bridging oxygen hole center—NBOHC).