43 research outputs found
Possibility to realize spin-orbit-induced correlated physics in iridium fluorides
Recent theoretical predictions of "unprecedented proximity" of the electronic
ground state of iridium fluorides to the SU(2) symmetric
limit, relevant for superconductivity in iridates, motivated us to investigate
their crystal and electronic structure. To this aim, we performed
high-resolution x-ray powder diffraction, Ir L-edge resonant inelastic
x-ray scattering, and quantum chemical calculations on Rb[IrF] and
other iridium fluorides. Our results are consistent with the Mott insulating
scenario predicted by Birol and Haule [Phys. Rev. Lett. 114, 096403 (2015)],
but we observe a sizable deviation of the state from the
SU(2) symmetric limit. Interactions beyond the first coordination shell of
iridium are negligible, hence the iridium fluorides do not show any magnetic
ordering down to at least 20 K. A larger spin-orbit coupling in iridium
fluorides compared to oxides is ascribed to a reduction of the degree of
covalency, with consequences on the possibility to realize spin-orbit-induced
strongly correlated physics in iridium fluorides
Global occurrence, chemical properties, and ecological impacts of e-wastes (IUPAC technical report)
The waste stream of obsolete electronic equipment grows exponentially, creating a worldwide pollution and resource problem. Electrical and electronic waste (e-waste) comprises a heterogeneous mix of glass, plastics (including flame retardants and other additives), metals (including rare earth elements) and metalloids. The e-waste issue is complex and multi-faceted. In examining the different aspects of e-waste, informal recycling in developing countries has been identified as a primary concern due to widespread illegal shipments, weak environmental as well as health and safety regulations, lack of technology and inadequate waste treatment structure. For example, Nigeria, Ghana, India, Pakistan and China have all been identified as hotspots for the disposal of e-waste. This article presents a critical examination on the chemical nature of e-waste and the resulting environmental impacts on, for example, microbial biodiversity, flora and fauna in e-waste recycling sites around the world. It highlights the different types of risk assessment approaches required when evaluating the ecological impact of e-waste. Additionally, it presents examples of chemistry playing a role in potential solutions. The information presented here will be informative to relevant stakeholders to devise integrated management strategies to tackle this global environmental concern
A realistic in silico model for structure/function studies of molybdenum–copper CO dehydrogenase
CO dehydrogenase (CODH) is an environmentally crucial bacterial enzyme that oxidizes CO to CO2 at a Mo–Cu active site. Despite the close to atomic resolution structure (1.1 Å), significant uncertainties have remained with regard to the protonation state of the water-derived equatorial ligand coordinated at the Mo-center, as well as the nature of intermediates formed during the catalytic cycle. To address the protonation state of the equatorial ligand, we have developed a realistic in silico QM model (~179 atoms) containing structurally essential residues surrounding the active site. Using our QM model, we examined each plausible combination of redox states (MoVI–CuI, MoV–CuII, MoV–CuI, and MoIV–CuI) and Mo-coordinated equatorial ligands (O2−, OH−, H2O), as well as the effects of second-sphere residues surrounding the active site. Herein, we present a refined computational model for the Mo(VI) state in which Glu763 acts as an active site base, leading to a MoO2-like core and a protonated Glu763. Calculated structural and spectroscopic data (hyperfine couplings) are in support of a MoO2-like core in agreement with XRD data. The calculated two-electron reduction potential (E = −467 mV vs. SHE) is in reasonable agreement with the experimental value (E = −558 mV vs. SHE) for the redox couple comprising an equatorial oxo ligand and protonated Glu763 in the MoVI–CuI state and an equatorial water in the MoIV–CuI state. We also suggest a potential role of second-sphere residues (e.g., Glu763, Phe390) based on geometric changes observed upon exclusion of these residues in the most plausible oxidized states
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The behaviour of organic solvents containing C5-BTBP and CyMe4-BTBP at low irradiation doses
Low doses of gamma radiation were given to four different solvents containing C5-BTBP and CyMe4-BTBP, each molecule dissolved both in cyclohexanone and hexanol. Four corresponding solvents were kept unirradiated and used as references for the extraction experiments. Multiple samples were taken from both the irradiated solutions and the reference solutions at certain time intervals. The samples were used in extraction experiments with the radionuclides Am-241 and Eu-152. The protection against radiolysis of the extracting molecules by the diluent used for dissolution without adding a scavenger molecule was checked. The interplay between the diluent and the side group of the extracting molecule for protection against radiolysis was also studied by keeping the same type of core molecule for binding to the metal ions and varying the diluent and side group. The results were unexpected. The presence of a cyclic molecule as both a side group or diluent seems to keep the extraction of europium almost unaffected by radiolysis, while americium behaves differently from solvent to solvent. The diluent alone does not protect the extracting molecule. In some of the studied systems there is a distinct change in the extraction behaviour of Am between the irradiated and reference solutions, an effect that is however only present at the beginning of the experimental series. At later times the difference in distribution ratios between the irradiated and reference solution is constant. This phenomenon is found only when the side group and diluent are structurally dissimilar
Influence of dose rate on the radiolytic stability of a BTBP solvent for actinide(III)/lanthanide(III) separation
The recently developed ligand MF2-BTBP dissolved in cyclohexanone is a promising solvent for the group separation of trivalent actinides(Ill) from the lanthanides(Ill). Its high stability against nitric acid has been demonstrated recently. Since the solvent is also exposed to a continuously high radiation level in the counter current process, the radiolytic stability of the solvent was examined in this study. Irradiation experiments were carried out up to an absorbed dose of 100 kGy and the effect of the dose rate was investigated. The extraction behaviour for An(III)/Ln(III) separation was studied after radiolysis for evaluation. It was found that during high dose rate irradiation the extraction efficiency for both Am(III) and Eu(III) decreased significantly with increasing absorbed dose, whereas during the low dose rate irradiation the extraction efficiencies remained more or less at the same level
Influence of dose rate on the radiolytic stability of a BTBP solvent for actinide(III)/lanthanide(III) separation
The recently developed ligand MF2-BTBP dissolved in cyclohexanone is a promising solvent for the group separation of trivalent actinides(Ill) from the lanthanides(Ill). Its high stability against nitric acid has been demonstrated recently. Since the solvent is also exposed to a continuously high radiation level in the counter current process, the radiolytic stability of the solvent was examined in this study. Irradiation experiments were carried out up to an absorbed dose of 100 kGy and the effect of the dose rate was investigated. The extraction behaviour for An(III)/Ln(III) separation was studied after radiolysis for evaluation. It was found that during high dose rate irradiation the extraction efficiency for both Am(III) and Eu(III) decreased significantly with increasing absorbed dose, whereas during the low dose rate irradiation the extraction efficiencies remained more or less at the same level
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Extraction behavior of nickel(II) using some of the BTBP-class ligands
Recently the BTBP-family of solvating ligands have been studied for their ability to separate trivalent actinides from lanthanides. Five of the BTBPs were evaluated for their ability to extract nickel(II) from aqueous nitrate media into cyclohexanone. It was shown by both solvent extraction and X-ray diffraction experiments that the BTBPs are capable of forming both 1: 1 and 1:2 complexes with nickel(II). When the BTBP concentration is low the nickel distribution ratio is governed by the formation of the nickel/BTBP complex while at higher BTBP concentrations the partitioning of the nickel complex between the two phases dictates the nickel distribution ratio