Modulating the effective ionic radii of trivalent dopants in ceria using a combination of dopants to improve catalytic efficiency for the oxygen evolution reaction.

Aliovalent doping in ceria and defect engineering are important aspects in tuning the properties of ceria for advanced technological applications, especially in the emerging field of electrocatalytic water-splitting for harvesting renewable energy. However, the ambiguity regarding the choice of dopants/co-dopants and ways to deal with the size difference between dopants and lattice hosts remains a long-standing problem. In this study, ceria was aliovalently codoped with Sc3+ and La3+ while keeping the total concentration of dopants constant; the ionic radius of the former is smaller and that of the latter is larger than Ce4+. Variations in the relative amounts of these dopants helped to modulate the effective ionic radii and match that of the host. A systematic study on the role of these aliovalent dopants in defect evolution in ceria and in modulating the Ce3+ fraction using powder XRD, Rietveld refinement, positron annihilation lifetime spectroscopy, X-ray photoelectron spectroscopy, Eu3+ photoluminescence, and Raman spectroscopy is presented here. The evolved defects and their dependence on subtle factors other than charge compensation are further correlated with their electrocatalytic activity towards oxygen evolution reaction (OER) in alkaline medium. The catalyst with an optimum defect density, maximum Ce3+ fraction at the surface and the least effective ionic radius difference between the dopants and the host demonstrated the best performance towards the OER. This study demonstrates how effective ionic radius modulation in defect-engineered ceria through a judicious choice of codopants can enhance the catalytic property of ceria and provides immensely helpful information for designing ceria-based heterogeneous catalysts with desired functionalities.

A single hydrogen bond that tunes flavin redox reactivity and activates it for modification.

Electron bifurcation produces high-energy products based on less energetic reagents. This feat enables biological systems to exploit abundant mediocre fuel to drive vital but demanding reactions, including nitrogen fixation and CO2 capture. Thus, there is great interest in understanding principles that can be portable to man-made devices. Bifurcating electron transfer flavoproteins (Bf ETFs) employ two flavins with contrasting reactivities to acquire pairs of electrons from a modest reductant, NADH. The bifurcating flavin then dispatches the electrons individually to a high and a low reduction midpoint potential (E°) acceptor, the latter of which captures most of the energy. Maximum efficiency requires that only one electron accesses the exergonic path that will 'pay for' the production of the low-E° product. It is therefore critical that one of the flavins, the 'electron transfer' (ET) flavin, is tuned to execute single-electron (1e-) chemistry only. To learn how, and extract fundamental principles, we systematically altered interactions with the ET-flavin O2 position. Removal of a single hydrogen bond (H-bond) disfavored the formation of the flavin anionic semiquinone (ASQ) relative to the oxidized (OX) state, lowering by 150 mV and retuning the flavin's tendency for 1e-vs. 2e- reactivity. This was achieved by replacing conserved His 290 with Phe, while also replacing the supporting Tyr 279 with Ile. Although this variant binds oxidized FADs at 90% the WT level, the ASQ state of the ET-flavin is not stable in the absence of H290's H-bond, and dissociates, in contrast to the WT. Removal of this H-bond also altered the ET-flavin's covalent chemistry. While the WT ETF accumulates modified flavins whose formation is believed to rely on an anionic paraquinone methide intermediate, the FADs of the H-bond lacking variant remain unchanged over weeks. Hence the variant that destabilizes the anionic semiquinone also suppresses the anionic intermediate in flavin modification, verifying electronic similarities between these two species. These correlations suggest that the H-bond that stabilizes the crucial flavin ASQ also promotes flavin modification. The two effects may indeed be inseparable, as a Jekyll and Hydrogen bond.

Color tunable luminescence in ThO2:Er3+,Yb3+ nanocrystals: a promising new platform for upconversion.

Lanthanide-doped luminescent nanoparticles are an appealing system for many applications in the area of biomedical, solar cell, thermometry, anti-counterfeiting, etc. due to their sensitivity, reliability, high photochemical stability, and high optical transparency in the visible-NIR range. A color-tunable upconversion-luminescence (UCL) in a new low phonon energy ThO2 host based on modulating sensitizer concentration has been realized in this work and it may work as a potential candidate to replace corrosive and toxic fluoride based hosts in the future. Er3+-Yb3+ co-doped thoria nanoparticles were prepared using a gel combustion route and their structural and luminescence properties were determined as a function of the Yb3+ concentration. Phonon dispersion measurements have established the dynamic structural stability of the thoria nanoparticles. Density functional theory (DFT) was used to calculate the defect formation energy, highlighting the feasibility of dual ion (Er3+ and Yb3+) doping in thoria. The morphology and average size of the doped thoria was studied using high resolution transmission electron microscopy (HRTEM), and any defects evolving as a result of aliovalent doping were probed using positron annihilation lifetime spectroscopy (PALS). With 980 nm laser excitation, the nanothoria emits green and near-red light. A significant enhancement of the red-to-green intensity ratio of Er3+ ions in nanothoria was observed with an increase in Yb3+ concentration which resulted in beautiful color tunability from green to yellow light in going from lower (up to ∼5 mol%) to higher (10 and 15 mol%) Yb3+ concentration. The power dependence and the dynamics of the upconverted emission confirm the existence of two-photon upconversion processes for the green and red emissions.

Structure, dynamics, and redox reactivity of an all-purpose flavodoxin.

The flavodoxin of Rhodopseudomonas palustris CGA009 (Rp9Fld) supplies highly reducing equivalents to crucial enzymes such as hydrogenase, especially when the organism is iron-restricted. By acquiring those electrons from photodriven electron flow via the bifurcating electron transfer flavoprotein, Rp9Fld provides solar power to vital metabolic processes. To understand Rp9Fld's ability to work with diverse partners, we solved its crystal structure. We observed the canonical flavodoxin (Fld) fold and features common to other long-chain Flds but not all the surface loops thought to recognize partner proteins. Moreover, some of the loops display alternative structures and dynamics. To advance studies of protein-protein associations and conformational consequences, we assigned the 19F NMR signals of all five tyrosines (Tyrs). Our electrochemical measurements show that incorporation of 3-19F-Tyr in place of Tyr has only a modest effect on Rp9Fld's redox properties even though Tyrs flank the flavin on both sides. Meanwhile, the 19F probes demonstrate the expected paramagnetic effect, with signals from nearby Tyrs becoming broadened beyond detection when the flavin semiquinone is formed. However, the temperature dependencies of chemical shifts and linewidths reveal dynamics affecting loops close to the flavin and regions that bind to partners in a variety of systems. These coincide with patterns of amino acid type conservation but not retention of specific residues, arguing against detailed specificity with respect to partners. We propose that the loops surrounding the flavin adopt altered conformations upon binding to partners and may even participate actively in electron transfer.

γ-Resistant Microporous CAU-1 MOF for Selective Remediation of Thorium.

A simple solvothermal method was used to synthesize a metal-organic framework (MOF) with an Al metal entity, viz., CAU-1 NH2. The synthesized MOF was characterized using different techniques like X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy (SEM), field emission SEM (FE-SEM), transmission electron microscopy, small-angle X-ray scattering, positron annihilation lifetime spectroscopy, and X-ray photoelectron spectroscopy. The radiation stability was evaluated by irradiating the material up to a cumulative dose of 2 MGy using 60Co for the first time. The studies showed a remarkable gamma irradiation stability of the material up to 1 MGy. The porosity and surface area of the synthesized MOF were determined by Brunauer-Emmett-Teller, which showed a high specific surface area of 550 m2/g. The pH dependence study of Th uptake from an aqueous solution was performed from pH 2-8, followed by adsorption isotherm and adsorption kinetics studies. These results revealed that the Langmuir and pseudo-second-order kinetic models can be well adapted for understanding the Th uptake and kinetics, respectively. The synthesized MOF exhibited an ∼404 mg/g thorium adsorption capacity. Selectivity studies of adsorption of Th w.r.t. to U and different metal ions such as Cu, Co, Ni, and Fe showed that Th gets adsorbed preferentially as compared to other metal ions. In addition, the MOF could be used multiple times without much deterioration.

Askival: An altered feldspathic cumulate sample in Gale crater.

Askival is a light-toned, coarsely crystalline float rock, which was identified near the base of Vera Rubin Ridge in Gale crater. We have studied Askival, principally with the ChemCam instrument but also using APXS compositional data and MAHLI images. Askival and an earlier identified sample, Bindi, represent two rare examples of feldspathic cumulate float rocks in Gale crater with >65% relict plagioclase. Bindi appears unaltered whereas Askival shows textural and compositional signatures of silicification, along with alkali remobilization and hydration. Askival likely experienced multiple stages of alteration, occurring first through acidic hydrolysis of metal cations, followed by deposition of silica and possible phyllosilicates at low T and neutral-alkaline pH. Through laser-induced breakdown spectroscopy compositional analyses and normative calculations, we suggest that an assemblage of Fe-Mg silicates including amphibole and pyroxene, Fe phases, and possibly Mg-rich phyllosilicate are present. Thermodynamic modeling of the more pristine Bindi composition predicts that amphibole and feldspar are stable within an upper crustal setting. This is consistent with the presence of amphibole in the parent igneous rocks of Askival and suggests that the paucity of amphiboles in other known Martian samples reflects the lack of representative samples of the Martian crust rather than their absence on Mars.

Oxygen vacancy and valence engineering in CeO2 through distinct sized ion doping and their impact on oxygen reduction reaction catalysis.

Defect tuning in ceria to enhance its catalytic properties is a subject of great interest for the scientific community owing to the growing demand for catalytic materials in drug, automobile and chemical industries. Doping induced defect engineering was found to be one of the most sought out strategies particularly in oxides for achieving multifunctionality. Here, in this study, we have doped ceria with distinct sized trivalent rare-earth ions, namely, Y3+, Eu3+ and La3+, using combustion techniques. Positron annihilation lifetime spectroscopy (PALS) suggested enhanced defect density with doping in general and higher concentration of oxygen vacancies in La3+ doped ceria compared to Y3+ and Eu3+ counterparts. X-ray photoelectron spectroscopy (XPS) suggested the existence of both Ce3+ and Ce4+, with the former having higher fraction in CeO2:La3+ compared to CeO2:Y3+. The electron transfer resistance (Rct) reduced in all the doped samples when compared to undoped ceria and they demonstrated improved catalytic activity towards the oxygen reduction reaction (ORR). The highest reduction in Rct was seen in the 5% La doped sample owing to the very high concentration of oxygen vacancies and Ce3+/Ce4+ ratio and CeO2:5.0% La3+ showed the best performance towards ORR electrocatalysis. The studies are expected to help in further tuning the catalysts in terms of dopant concentrations, and in future work, the strategy will be to control the Ce3+/Ce4+ ratio and see its implication in both catalytic and magnetic applications.

Tailoring defect structure and dopant composition and the generation of various color characteristics in Eu3+ and Tb3+ doped MgF2 phosphors.

A novel approach to generate a wide range of color characteristics such as near white, yellow, orange and red in MgF2, by proper tailoring of the defect structure and varying the composition of Eu3+ and Tb3+ dopant ions have been presented here. It has been observed from positron annihilation lifetime spectroscopy (PALS) study that various defect centers such as mono vacancies and their cluster forms exist in the system, whose amount varies upon varying the dopant ion's composition. The experimentally observed positron lifetime values of the defect centers also matched well with the theoretically calculated lifetime values using the MIKA-DOPPLER package. It has been found that a few vacancies or defect centers act as color centers, while the cluster vacancies change the local symmetry of the rare earth ion by inducing more distortion surrounding them thereby resulting in different emission characteristics in the photoluminescence (PL) study. The defect-related host emission in combination with the green and red emission from Tb3+ and Eu3+ ions generated near-white-light in some of the compounds, while other compounds showed a variety of other color characteristics due to the Tb3+ → Eu3+energy transfer dynamics. The various defect-related emissions, the role of the defect-related trap state in the decay kinetics and the energy-transfer dynamics were also understood by analyzing the electronic structure using HSE06 hybrid functional calculation.

Defect engineering in trivalent ion doped ceria through vanadium assisted charge compensation: insight using photoluminescence, positron annihilation and electron spin resonance spectroscopy.

Pair matching charge compensation with trivalent and pentavalent dopants in ceria was found to be an attractive strategy in engineering defects with minimal distortions in the lattice and obtaining enhanced catalytic properties. In the present study, charge compensation with a vanadium codopant in trivalent ion doped ceria is studied. Defect evolution in the trivalent ion doped ceria with vanadium codoping has been studied in CeO2:Eu3+, CeO2:La3+,Eu3+ and CeO2:Y3+,Eu3+ systems and the choices of the dopant and co-dopant are triggered by their ionic radius. Eu3+ photoluminescence (PL) is used as a spectroscopic probe to monitor local structural changes around the dopants. Positron lifetime studies showed that oxygen vacancies formed due to trivalent ion doping are weakly associated when larger ions are doped and result in the formation of vacancy aggregates. Positron lifetime studies along with XRD studies show that vanadium codoping effectively removes the vacancies but the distortions are significant when the size mismatch between the pair match used for charge compensation is higher. Photoluminescence demonstrated that the oxygen vacancies associated with Eu are more effectively removed in the case of Y codoped samples. Electron Spin Resonance (ESR) studies suggested that vanadium in excess over the stoichiometric concentration of the trivalent ion can lead to additional defects. These studies are expected to help in tuning the vacancy concentrations as well as controlling the lattice distortions for technological applications such as catalysis, ionic conductivity, etc.

Multiphoton light emission in barium stannate perovskites driven by oxygen vacancies, Eu3+ and La3+: accessing the role of defects and local structures.

Defect engineering in perovskites has been found to be the most efficient approach to manipulate their performance in ultraviolet-to-visible photon conversion. Under UV irradiation, BaSnO3 exhibited multicolor photoluminescence (MCPL) in the bluish white region. Its origin has not been well studied in the literature and has been probed in this work using synchrotron radiation, positron annihilation and density functional theory. To achieve desirable performance of doped BaSnO3 in optoelectronics, it is imperative to have correct information on the dopant local site, doping induced defect evolution and efficacy of host to dopant energy transfer (HDET). Extended X-ray absorption fine structure (EXAFS) showed that Eu3+ ions stabilize at both Ba2+ and Sn4+ sites consistent with the highly negative formation energy of around -6.26 eV. Eu3+ doping leads to an intense 5D0→7F1 orange emission and a feeble 5D0→7F2 red emission and an internal quantum yield (IQY) of ∼21% mediated by ET from the defect level of EuBa and EuSn sites to the valence band maximum (VBM). X-ray absorption near edge structure (XANES) ruled out any role of Sn2+ in the PL of BaSnO3 or Eu2+ in the PL of BaSnO3:Eu3+. Interestingly, when co-doped, Eu3+ stabilizes at Sn4+ sites whereas La3+ stabilizes at Ba2+ sites with a formation energy value of -6.44 eV. Based on the asymmetry ratio in emission spectra, it was found that La3+ ions lead to lowering of symmetry around Eu3+ due to increased vacancies and structural distortions, and also suppress the luminescence IQY. We have performed experimental positron annihilation lifetime spectroscopy (PALS) to probe the defects in BaSnO3 in pristine samples and on doping/co-doping. The positron lifetimes for saturation trapping of positrons in various kinds of defects envisaged in BaSnO3 and in the defect free system were calculated using the MIKA Doppler program. Such deep insight into the effect of local structures, dopant sites, defect evolution, ET, etc. on the optical properties of BaSnO3 is expected to provide very deep insight for material scientists into the fabrication of perovskite-based optoelectronic and light-emitting devices.

Studies on leaching characteristics of electronic waste for metal recovery using inorganic and organic acids and base.

In this paper, we report leaching of precious and scattered metals such as gold (Au), copper (Cu), nickel (Ni), zinc (Zn), iron (Fe), and lead (Pb) from printed circuit boards of scrap mobile phones by hydrometallurgical process using inorganic acid, organic acid and base. The amount of metals leached by different leachants are quantified using atomic absorption spectroscopy. Among various inorganic acids, aqua regia (mixture of nitric acid (HNO3) and hydrochloric acid) is found to be the strongest leachant for most of the metals such as Zn (2.04 wt %), Fe (17.90 wt %), Ni (0.66 wt %), Pb (5.86 wt %) and Au (0.04 wt %). The basic leachant, ammonium thiosulphate is found to be very effective in leaching of Au (0.03125 wt %). The dissolution of Cu in HNO3 gives the highest amount of Cu in the solvent, that is, ∼ 7.52 wt %. The metallic phases present in the electronic waste before and after leaching are identified by X-ray diffraction analysis. The microscopic structure has been studied using a scanning electron microscope which depicts erosion of the structure after leaching.

Engineering defect clusters in distorted NaMgF3 perovskite and their important roles in tuning the emission characteristics of Eu3+ dopant ion.

An attempt has been made to explore various new defect clusters in distorted NaMgF3 perovskite and their important role in tuning optical properties. We have tried to tailor the defect clusters and to understand the impact on the luminescence of the lanthanide, for example the Eu3+ ion. Defect engineering has been carried out by doping aliovalent dopant ions to create a charge imbalance in the matrix, which in turn led to the creation of various mono-, di- and new cluster vacancies. Such vacancies have been characterized by Electron Para-magnetic Resonance (EPR), Positron Annihilation Lifetime Spectroscopy (PALS) and Photoluminescence (PL) studies. The PALS data of both undoped and Eu3+ doped compounds confirmed that in addition to Mg mono vacancies, cluster vacancies with different configurations comprising Mg, Na and F atom vacancies also exist in the matrix. The PL study revealed that depending on the surrounding defect structure, three different types of Eu3+ components can be created. The position of the Eu3+ ion with respect to these cluster vacancies determines the respective emission profiles and the decay kinetics. It has been found that when Li+ ions are co-doped with Eu3+, there is a sudden change in the decay kinetics and the emission profiles. The PALS study revealed that Li+ co-doping modified the configuration of the vacancy clusters, which in turn changes the emission characteristics. The EPR study confirmed the presence of different types of F-centers (F, F2, etc.) which are responsible for the host emission. Overall, this new study will be very helpful for a detailed understanding of the defect structures, in particular the cluster vacancies in distorted NaMgF3 perovskite, which have a direct or indirect impact on many physical properties.

Unilateral versus bilateral spinal anaesthesia in geriatric patients undergoing hemiarthroplasty: a comparative study.

INTRODUCTION: Conventional bilateral spinal anaesthesia can produce haemodynamic alterations that can be detrimental to geriatric patients. Unilateral spinal anaesthesia produces predominant blockade on the operated side, thereby reducing the incidence of hypotension. There is a scarcity of comparative studies evaluating the effects of unilateral spinal anaesthesia in the elderly population. Therefore, we conducted this study to compare the effects of unilateral and bilateral spinal anaesthesia in geriatric patients. MATERIAL AND METHODS: A prospective, parallel group, randomized, controlled study was conducted on 72 patients of age 60-85 years, ASA physical status I and II undergoing hemiarthroplasty under spinal anaesthesia. Patients were randomly allocated to two groups: patients in group U (n = 36) received unilateral spinal anaesthesia, those in group B (n = 36) received bilateral spinal anaesthesia. All patients received 1.5 mL of hyperbaric bupivacaine (0.5%) and 0.5 mL of fentanyl intrathecally in the lateral decubitus position. Patients in group B were turned to the supine position and those in group U maintained the lateral decubitus position for 15 minutes. Intraoperative and postoperative haemodynamic parameters, Bromage score and sensory block height were compared. RESULTS: Hypotension in group B patient was more pronounced compared to group U. There was no significant difference in the Bromage score and the number of patients reaching T10 sensory block height on the operated side between the two groups. The Bromage score and the number of patients reaching T10 sensory block height on the non-operated side were higher in group B. CONCLUSIONS: In geriatric patients unilateral spinal anaesthesia produces predominant motor and sensory block on the operated side with less hypotension.