Ralph Steininger

Bridging the efficiency gap: fully bridged dinuclear Cu(I)-complexes for singlet harvesting in high-efficiency OLEDs.

The substitution of rare metals such as iridium and platinum in light-emitting materials is a key step to enable low-cost mass-production of organic light-emitting diodes (OLEDs). Here, it is demonstrated that using a solution-processed, fully bridged dinuclear Cu(I)-complex can yield very high efficiencies. An optimized device gives a maximum external quantum efficiency of 23 ± 1% (73 ± 2 cd A(-1) ).

A mineralogical, geochemical, and microbiogical assessment of the antimony- and arsenic-rich neutral mine drainage tailings near Pezinok, Slovakia

Abstract The mineralogical composition of mining wastes deposited in voluminous tailing impoundments around the world is the key factor that controls retention and release of pollutants. Here we report a detailed mineralogical, geochemical, and microbiological investigation of two tailing impoundments near the town of Pezinok, Slovakia. The primary objective of this study was the mineralogy that formed in the impoundment after the deposition of the tailings (so-called tertiary minerals). Tertiary minerals include oxyhydroxides of Fe, Sb, As, Ca and are present as grains and as rims on primary ore minerals. X-ray microdiffraction data show that the iron oxyhydroxides with abundant As are X-ray amorphous. The limiting (lowest) Fe/As (wt/wt%) ratio in this material is 1.5; beyond this ratio, the hydrous ferric oxide does not retain arsenic. The grains with less As and little to moderate amounts of Sb are goethite; the grains where Sb dominates over Fe are poorly crystalline tripuhyite (FeSbO4). Even the most heavily contaminated samples (up to 29 wt% As2O5) are populated with diverse communities of microorganisms including typical arsenic-resistant heterotrophic species as well as iron reducers and sulfur oxidizers. Several recovered clones cluster within phylogenetic groups that are solely based on environmental sequences and do not contain a single cultivated species, thus calling for more work on such extreme environments.

Labile or Stable: Can Homoleptic and Heteroleptic PyrPHOS–Copper Complexes Be Processed from Solution?

Luminescent Cu(I) complexes are interesting candidates as dopants in organic light-emitting diodes (OLEDs). However, open questions remain regarding the stability of such complexes in solution and therefore their suitability for solution processing. Since the emission behavior of Cu(I) emitters often drastically differs between bulk and thin film samples, it cannot be excluded that changes such as partial decomposition or formation of alternative emitting compounds upon processing are responsible. In this study, we present three particularly interesting candidates of the recently established copper-halide-(diphenylphosphino)pyridine derivatives (PyrPHOS) family that do not show such changes. We compare single crystals, amorphous bulk samples, and neat thin films in order to verify whether the material remains stable upon processing. Solid-state nuclear magnetic resonance (MAS (31)P NMR) was used to investigate the electronic environment of the phosphorus atoms, and X-ray absorption spectroscopy at the Cu K edge provides insight into the local electronic and geometrical environment of the copper(I) metal centers of the samples. Our results suggest that--unlike other copper(I) complexes--the copper-halide-PyrPHOS clusters are significantly more stable upon processing and retain their initial structure upon quick precipitation as well as thin film processing.

Location and Electronic Nature of Phosphorus in the Si Nanocrystal--SiO2 System.

Up to now, no consensus exists about the electronic nature of phosphorus (P) as donor for SiO2-embedded silicon nanocrystals (SiNCs). Here, we report on hybrid density functional theory (h-DFT) calculations of P in the SiNC/SiO2 system matching our experimental findings. Relevant P configurations within SiNCs, at SiNC surfaces, within the sub-oxide interface shell and in the SiO2 matrix were evaluated. Atom probe tomography (APT) and its statistical evaluation provide detailed spatial P distributions. For the first time, we obtain ionisation states of P atoms in the SiNC/SiO2 system at room temperature using X-ray absorption near edge structure (XANES) spectroscopy, eliminating structural artefacts due to sputtering as occurring in XPS. K energies of P in SiO2 and SiNC/SiO2 superlattices (SLs) were calibrated with non-degenerate P-doped Si wafers. results confirm measured core level energies, connecting and explaining XANES spectra with h-DFT electronic structures. While P can diffuse into SiNCs and predominantly resides on interstitial sites, its ionization probability is extremely low, rendering P unsuitable for introducing electrons into SiNCs embedded in SiO2. Increased sample conductivity and photoluminescence (PL) quenching previously assigned to ionized P donors originate from deep defect levels due to P.

Structural Incorporation of As5+ into Hematite

Hematite (α-Fe2O3) is one of the most common iron oxides and a sink for the toxic metalloid arsenic. Arsenic can be immobilized by adsorption to the hematite surface; however, the incorporation of As in hematite was never seriously considered. In our study we present evidence that, besides adsorption, the incorporation of As into the hematite crystals can be of great relevance for As immobilization. With the coupling of nanoresolution techniques and X-ray absorption spectroscopy the presence of As (up to 1.9 wt %) within the hematite crystals could be demonstrated. The incorporated As(5+) displays a short-range order similar to angelellite-like clusters, epitaxially intergrown with hematite. Angelellite (Fe4As2O11), a triclinic iron arsenate with structural relations to hematite, can epitaxially intergrow along the (210) plane with the (0001) plane of hematite. This structural composite of hematite and angelellite-like clusters represents a new immobilization mechanism and potentially long-lasting storage facility for As(5+) by iron oxides.

Thallium speciation and extractability in a thallium- and arsenic-rich soil developed from mineralized carbonate rock

We investigated the speciation and extractability of Tl in soil developed from mineralized carbonate rock. Total Tl concentrations in topsoil (0-20 cm) of 100-1000 mg/kg are observed in the most affected area, subsoil concentrations of up to 6000 mg/kg Tl in soil horizons containing weathered ore fragments. Using synchrotron-based microfocused X-ray fluorescence spectrometry (μ-XRF) and X-ray absorption spectroscopy (μ-XAS) at the Tl L3-edge, partly Tl(I)-substituted jarosite and avicennite (Tl2O3) were identified as Tl-bearing secondary minerals formed by the weathering of a Tl-As-Fe-sulfide mineralization hosted in the carbonate rock from which the soil developed. Further evidence was found for the sequestration of Tl(III) into Mn-oxides and the uptake of Tl(I) by illite. Quantification of the fractions of Tl(III), Tl(I)-jarosite and Tl(I)-illite in bulk samples based on XAS indicated that Tl(I) uptake by illite was the dominant retention mechanism in topsoil materials. Oxidative Tl(III)uptake into Mn-oxides was less relevant, probably because the Tl loadings of the soil exceeded the capacity of this uptake mechanism. The concentrations of Tl in 10 mM CaCl2-extracts increased with increasing soil Tl contents and decreasing soil pH, but did not exhibit drastic variations as a function of Tl speciation. With respect to Tl in contaminated soils, this study provides first direct spectroscopic evidence for Tl(I) uptake by illite and indicates the need for further studies on the sorption of Tl to clay minerals and Mn-oxides and its impact on Tl solubility in soils.

Selenium distribution and speciation in plant parts of wheat (Triticum aestivum) and Indian mustard (Brassica juncea) from a seleniferous area of Punjab, India

The concentration, distribution, and speciation of selenium in different parts of wheat and Indian mustard, grown in a seleniferous area in Punjab, were investigated using synchrotron based (XAS) and classical acid digestion and extraction methods. The analyses revealed a high Se enrichment in all investigated plant parts, with Se levels in the range of 133-931 mg/kg (dry weight, dw). Such high Se enrichment is mainly due to the considerable amounts of easily available Se detected in the soil, which are renewed on a yearly basis to some extent via irrigation. Speciation analysis in soil and plants indicated selenate and organic Se as major Se species taken up by plants, with a minor presence of selenite. The analyses also revealed that the highest Se enrichment occurs in the upper plant parts, in agreement with the high uptake rate and mobility of selenate within plants. In both wheat and mustard, highest Se enrichments were found in leaves (387 mg/kg·dw in wheat and 931 mg/kg·dw in mustard). Organic species (dimethylselenide and methylselenocysteine) were found in different parts of both plants, indicating that an active detoxification response to the high Se uptake is taking place through methylation and/or volatilization. The high proportion of selenate in wheat and mustard leaves (47% and 70%, respectively) is the result of the inability of the plant metabolism to completely transform selenate to non-toxic organic forms, if oversupplied. Methylselenocysteine, a common Se species in accumulating plants, was detected in wheat, suggesting that, in the presence of high Se concentration, this plant develops similar response mechanisms to accumulator plants.

Assessment of chemical species of lead accumulated in tidemarks of human articular cartilage by X-ray absorption near-edge structure analysis.

Lead is a toxic trace element that shows a highly specific accumulation in the transition zone between calcified and non-calcified articular cartilage, the so-called ‘tidemark’. Excellent agreement has been found between XANES spectra of synthetic Pb-doped carbonated hydroxyapatite and spectra obtained in the tidemark region and trabecular bone of normal human samples, confirming that in both tissues Pb is incorporated into the hydroxyapatite crystal structure of bone. During this study the µ-XANES set-up at the SUL-X beamline at ANKA was tested and has proven to be well suited for speciation of lead in human mineralized tissue samples.

Solid-phase characterisation of an effective household sand filter for As, Fe and Mn removal from groundwater in Vietnam

HouseholdsandfiltersarewidelyusedinVietnamtoremoveAs,FeandMnfromanoxicgroundwaterusedas a drinking water resource. To expand the mechanistic knowledge of the filter functioning, we investigated the bulk and micrometre-scale distribution of Fe, As, P and Mn and the speciation of Fe, Mn and As in a sand filter after 8 years of operation using bulk and micro-focussed X-ray fluorescence spectrometry (XRF) and X-ray absorption spectroscopy (XAS) and scanning electron microscopy coupled with energy dispersive X-ray detection (SEM-EDX). Effective oxygenation of the anoxic groundwater enables the oxidative removal of Fe, As and Mn in the filter sand. Our results show that Fe is retained in the filter as a 2-line ferrihydrite-like Fe III -precipitate that coats sand grains, and that As accumulates dominantly as pentavalent arsenate. The very close spatial correlation of accumulated As and P with Fe throughout the filter sand and down to the micrometre-scale and the effective Fe, P and As retention at an estimated average water residence time of only 30 min suggest that their uptake is governed by a combination of fast sorption reactions,surface-catalysedFe II oxidationandmediatedAs III co-oxidation.Incontrast,MnisretainedinseparateMn IV/III - (oxyhydr)oxide coatings and concretions, probably as a result of coupled surface-catalysed and microbial Mn II oxidation. Silicatesorbedtotheferrihydrite-likeFe III -coatingsinhibitstheircrystallisationandassociatedremobilisationofPandAs. The periodic drainage and aeration of the filter favours the oxidation of any residual Fe II and As III and the formation of

The role of nano-perovskite in the negligible thorium release in seawater from Greek bauxite residue (red mud)

We present new data about the chemical and structural characteristics of bauxite residue (BR) from Greek Al industry, using a combination of microscopic, analytical, and spectroscopic techniques. SEM-EDS indicated a homogeneous dominant “Al-Fe-Ca-Ti-Si-Na-Cr matrix”, appearing at the microscale. The bulk chemical analyses showed considerable levels of Th (111 μg g−1), along with minor U (15 μg g−1), which are responsible for radioactivity (355 and 133 Bq kg−1 for 232Th and 238U, respectively) with a total dose rate of 295 nGy h−1. Leaching experiments, in conjunction with SF-ICP-MS, using Mediterranean seawater from Greece, indicated significant release of V, depending on S/L ratio, and negligible release of Th at least after 12 months leaching. STEM-EDS/EELS & HR-STEM-HAADF study of the leached BR at the nanoscale revealed that the significant immobility of Th4+ is due to its incorporation into an insoluble perovskite-type phase with major composition of Ca0.8Na0.2TiO3 and crystallites observed in nanoscale. The Th LIII-edge EXAFS spectra demonstrated that Th4+ ions, which are hosted in this novel nano-perovskite of BR, occupy Ca2+ sites, rather than Ti4+ sites. That is most likely the reason of no Th release in Mediterranean seawater.