Electrocatalytic OER behavior of the Bi-Fe-O system: an understanding from the perspective of the presence of oxygen vacancies.

This study aims to understand and correlate the role of the nature and relative concentration of oxygen vacancies with the trend observed in the OER with the Bi-Fe-O system. To understand this, we first investigated the system of oxides using X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), which revealed the presence of oxygen vacancies in the system. Density functional theory (DFT) was employed to investigate the relative concentration of these vacancies by calculating their formation energies. Positron annihilation lifetime spectroscopy (PALS) was carried out to understand the nature of these oxygen vacancies. We observed that the presence of a higher concentration of monovacancies created due to the absence of oxygen from the structure of Bi2Fe4O9 was mainly responsible for the high performance of the oxide towards the OER compared to that of the other oxides viz-BiFeO3 and Bi25FeO40 of the Bi-Fe-O system.

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.

Role of plant neurotransmitters in salt stress: A critical review.

Neurotransmitters are naturally found in many plants, but the molecular processes that govern their actions still need to be better understood. Acetylcholine, γ-Aminobutyric acid, histamine, melatonin, serotonin, and glutamate are the most common neurotransmitters in animals, and they all play a part in the development and information processing. It is worth noting that all these chemicals have been found in plants. Although much emphasis has been placed on understanding how neurotransmitters regulate mood and behaviour in humans, little is known about how they regulate plant growth and development. In this article, the information was reviewed and updated considering current thinking on neurotransmitter signaling in plants' metabolism, growth, development, salt tolerance, and the associated avenues for underlying research. The goal of this study is to advance neurotransmitter signaling research in plant biology, especially in the area of salt stress physiology.

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.

ZnAl2O4:Er3+ Upconversion Nanophosphor for SPECT Imaging and Luminescence Modulation via Defect Engineering.

This work reports an "all-in-one" theranostic upconversion luminescence (UCL) system having potential for both diagnostic and therapeutic applications. Despite considerable efforts in designing upconversion nanoparticles (UCNPs) for multimodal imaging and tumor therapy, there are few reports investigating dual modality SPECT/optical imaging for theranostics. Especially, research focusing on in vivo biodistribution studies of intrinsically radiolabeled UCNPs after intravenous injection is of utmost importance for the potential clinical translation of such formulations. Here, we utilized the gamma emission from 169Er and 171Er radionuclides for the demonstration of radiolabeled ZnAl2O4:171/169Er3+ as a potent agent for dual-modality SPECT/optical imaging. No uptake of radio nanoformulation was detected in the skeleton after 4 h of administration, which evidenced the robust integrity of ZnAl2O4:169/171Er3+. Combining the therapeutics using the emission of ß- particulates from 169Er and 171Er will be promising for the radio-theranostic application of the synthesized ZnAl2O4:169/171Er3+ nanoformulation. Cell toxicity studies of ZnAl2O4:1%Er3+ nanoparticles were examined by an MTT assay in B16F10 mouse melanoma cell lines, which demonstrated good biocompatibility. In addition, we explored the mechanism of UCL modulation via defect engineering by Bi3+ codoping in the ZnAl2O4:Er3+ upconversion nanophosphor. The UCL color tuning was successfully achieved from the red to the green region as a function of Bi3+ codoping concentrations. Further, we tried to establish a correlation of UCL tuning with the intrinsic oxygen and cation vacancy defects as a function of Bi3+ codoping concentrations with the help of electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) studies. This study contributes to building a bridge between nature of defects and UC luminescence that is crucial for the design of advanced UCNPs for theranostics.

Oxygen vacancy-enriched Zn2SnO4 for aliphatic alcohol sensing and enhanced selectivity towards n-butanol.

The sensitive detection of toxic flammable volatile organics using low cost efficient sensors is important for ensuring both indoor and outdoor safety. It is essential for chemical sensors to exhibit a significantly stronger response to target analytes compared to equivalent amounts of analogous competing chemicals. In line with this importance, current work evaluated the performance of Zn2SnO4, a n-type semiconducting metal oxide, for sensing n-butanol in comparison to methanol, ethanol, and propanol vapours. These vapours fall within the category of aliphatic alcohols but vary in characteristics such as molecular weight, vapour pressure, volatility, and diffusivity. In this work we have explored the sensor's performance by adjusting the operating temperature over the range of 225-300 °C while detecting 1000 ppm of each of these vapours. Efforts were made to establish a correlation between the sensor's responses with the interactions of these vapours on the sensor's surface. Prior to assessing the sensing characteristics of the solid-state-route-derived Zn2SnO4, its structural characteristics, including phase purity, crystalline structure, bonding patterns, morphology, and defect characteristics, were studied. This comprehensive analysis sheds light on the potential of Zn2SnO4 as an effective sensor for detecting n-butanol.

Autocombustion Route Derived Zinc Ferrite Nanoparticles as Chemiresistive Sensor for Detection of Alcohol Vapors.

Prolonged exposure to alcohol vapors can have detrimental effects on human health, potentially leading to eye irritation, dizziness, and in some cases, damage to the nervous system. The present article aims to provide a comprehensive understanding on the synthesis and characterization of zinc ferrite (ZnFe2O4) nanoparticles, as well as their interactions with a range of alcohol vapors, including methanol, ethanol, n-propanol, and isopropanol. These alcohols differ in their molecular weight, boiling points, diffusivity, and other properties. The study reveals the semiconducting ZnFe2O4 nanoparticulate sensor's capability for reversible, repeatable, and sensitive detection of alcohol vapors. The sensor exhibits the highest response to ethanol within operating temperature range (225-300 °C). An attempt is made to establish a correlation between the properties of the target analytes and the observed sensing signals. Additionally, the response conductance transients of ZnFe2O4 under the exposure to the studied alcohol vapors are modeled based on the Langmuir-Hinshelwood adsorption mechanism. The characteristic time constants obtained from this modeling are justified with respect to the properties of the analytes.

Brachytherapy at the nanoscale with protein functionalized and intrinsically radiolabeled [169Yb]Yb2O3 nanoseeds.

PURPOSE: Classical brachytherapy of solid malignant tumors is an invasive procedure which often results in an uneven dose distribution, while requiring surgical removal of sealed radioactive seed sources after a certain period of time. To circumvent these issues, we report the synthesis of intrinsically radiolabeled and gum Arabic glycoprotein functionalized [169Yb]Yb2O3 nanoseeds as a novel nanoscale brachytherapy agent, which could directly be administered via intratumoral injection for tumor therapy. METHODS: 169Yb (T½ = 32 days) was produced by neutron irradiation of enriched (15.2% in 168Yb) Yb2O3 target in a nuclear reactor, radiochemically converted to [169Yb]YbCl3 and used for nanoparticle (NP) synthesis. Intrinsically radiolabeled NP were synthesized by controlled hydrolysis of Yb3+ ions in gum Arabic glycoprotein medium. In vivo SPECT/CT imaging, autoradiography, and biodistribution studies were performed after intratumoral injection of radiolabeled NP in B16F10 tumor bearing C57BL/6 mice. Systematic tumor regression studies and histopathological analyses were performed to demonstrate therapeutic efficacy in the same mice model. RESULTS: The nanoformulation was a clear solution having high colloidal and radiochemical stability. Uniform distribution and retention of the radiolabeled nanoformulation in the tumor mass were observed via SPECT/CT imaging and autoradiography studies. In a tumor regression study, tumor growth was significantly arrested with different doses of radiolabeled NP compared to the control and the best treatment effect was observed with ~ 27.8 MBq dose. In histopathological analysis, loss of mitotic cells was apparent in tumor tissue of treated groups, whereas no significant damage in kidney, lungs, and liver tissue morphology was observed. CONCLUSIONS: These results hold promise for nanoscale brachytherapy to become a clinically practical treatment modality for unresectable solid cancers.

Composition-dependent photoluminescence in nanocrystalline La2Hf2-xZrxO7:Eu phosphor: role of chemical twin Zr/Hf environments around a luminescent center.

Based on chemical intuition, linear trends are anticipated in Eu3+ photoluminescence performance inside a pyrochlore matrix of the chemical twins, Hf and Zr, owing to probable geometrical and chemical similarity around the luminescent center. The present work reports the drastically fluctuating result of doping Eu3+ in nanocrystalline pyrochlore, La2Hf2-xZrxO7 (LHZO), matrix on composition variation; the variation is counter to the anticipation-based chemical brotherhood of Hf and Zr. Zirconium-enriched samples of LHZO improve asymmetry around Eu3+ ion leading to enhanced photoluminescence quantum yield (PLQY). The samples with compositions 0.7Hf and 1.3Zr depict the lowest non-radiative channels with the highest theoretically calculated PLQY of ∼71% and excellent thermal stability (∼91%). Synergistic experimental and theoretical analysis reveals that Eu does not unbiasedly occupy La-sites in the pyrochlore LHZO matrix towards chemical twins of Hf and Zr; rather, it energetically prefers to occupy Zr-rich vicinal sites. When the composition with Zr is in the low-medium range, Eu has a higher probability of occupying Zr-rich vicinal sites depicting higher lifetime and PLQY. When Zr-content goes beyond 70-80%, the other site occupancies start contributing leading to a reduction in both lifetime and quantum yield. This work paves a great strategy and provides a futuristic potential to utilize europium luminescence in separating chemically close Hf-Zr for various technological applications.

Probing the p-type Chemiresistive Response of NiFe2 O4 Nanoparticles for Potential Utilization as Ethanol Sensor.

Detection of gas molecules and volatile organic compounds (VOCs) using efficient, low cost sensors has fetched significant attention in environmental monitoring, safety measures and medical diagnosis. In the present work, nickel ferrite (NFO) nanoparticles are explored as p-type semiconducting metal oxide (SMO) sensor for detection of five different organic vapors namely methanol, ethanol, n-propanol, iso-propanol and acetone which often cause severe damage to human body under prolonged exposure. The sensing studies in presence of the aforementioned five vapors are carried out by varying the sensor operating temperature (225-300 °C) and vapor concentrations (10-1000 ppm). Developed NFO sensor demonstrated best performance in terms of sensing (~10 ppm), response time (<10 s), excellent repeatability and selectivity towards ethanol among all other considered gas species. The repeatability of the sensor response is verified and the underlying reasons for the variation in the response of NFO sensor due to the change of operating temperature, analyte type and concentrations has been discussed. The synthesis of NFO through auto combustion method and study on their formation behaviour, oxygen vacancy evolution, band gap calculation, crystalline nature as well as microstructural features provides here the comprehensive information about the potential application of NFO nanoparticles as gas sensor.

Local Structure and Speciation-Driven UO22+ → Sm3+ Energy Transfer for Enhanced Luminescence in Li2B4O7.

Herein, we report the uranyl sensitization of Sm3+ emissions in uranium-codoped Li2B4O7:Sm3+ phosphor. The uranyl speciation in codoped [Sm, U] LTB samples was determined by synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy that revealed two coordination shells for U(VI) ions with bond distances of U-Oax (∼1.81 Å) and U-Oeq (∼2.30 Å). EXAFS fitting suggested that the uranyl moiety is present as pentagonal bipyramids (UO7) and hexagonal bipyramids (UO8) with five and six equatorial oxygen ligands, respectively. The alteration of the local structure of Sm3+ from [SmO4] to [SmO7] polyhedra and the changes in the coordination number of equatorial oxygen for uranyl were observed with different codoping concentrations of Sm3+ and uranium. Density functional theory (DFT) calculations suggested the lowering of defect formation energy for Li vacancies on codoping of Sm and U. Hence, we proposed the increase of the equatorial coordination number of UO22+ on the increase in the lithium vacancies in LTB. In addition, DFT supported the feasibility of efficient energy transfer (ET) due to the overlap of uranium and Sm3+ excited state levels. The influence of the same on the spectral features and UO22+ → Sm3+ energy transfer was investigated by time-resolved photoluminescence (PL) studies. The ET efficiency from the UO22+ to Sm3+ was 70.5% in 0.5 mol % codoped [Sm, U] LTB samples. The correlation of EXAFS and luminescence properties indicated a red shift in vibronic features of uranyl emission with increase in the equatorial coordination of the uranyl moiety from five to six. Additionally, a higher probability of ET was observed for uranyl speciation as UO8 hexagonal bipyramids. Temperature-dependent emissions and decay profiles were collected under uranyl excitation to investigate the thermal dependence of ET. A high energy barrier (Ea ∼ 4027 cm-1) was evaluated for the thermal quenching of Sm3+ emissions. This work provides insights into the modulation of luminescence and ET efficiency via structural changes in uranyl and Sm local environment in LTB phosphor.

ZnGa2-xAlxO4 (x = 0 ≤ 2) spinel for persistent light emission and HER/OER bi-functional catalysis.

Spinel materials have demonstrated diverse applications in various fields, especially in the energy sector. Since the pure spinel structure has the limitations of poor inherent activity and low conductivity, defect engineering through octahedral B-site modulation is expected to enhance various properties. Here in this work, we have synthesized ZnGa2-xAlxO4 (x = 0 ≤ 2) spinel and moved from one terminal (ZnGa2O4) to the other (ZnAl2O4) by varying the Ga/Al ratio using solvent-free solid-state reaction. Dopant and rare earth element-free (RE) ZnGa2O4 spinel showed excellent blue luminescence with photoluminescent quantum yields (PLQY) of 13% while exhibiting persistent light emission close to 60 min. The Al3+ incorporation at Ga3+ site doesn't yield any improvement in persistent luminescence lifetime owing to quenching of shallow traps as suggested by thermoluminescence (TL) studies. Moreover our materials have demonstrated bifunctional electrocatalytic activity towards both oxygen evolution (OER) and hydrogen evolution reaction (HER) which has never been reported for ZnGa2-xAlxO4. X-ray photoelectron spectroscopy (XPS) and positron annihilation lifetime spectroscopy (PALS) suggested that mixed Al/Ga-containing spinels possessed enhanced oxygen vacancies/defects. This makes them better electrocatalyst towards OER and HER compare to ZnGa2O4 and ZnAl2O4. The ZnGa1.75Al0.25O4 composition by virtue of enhanced oxygen vacancies and less charge transfer resistance (47.3 ohms) demonstrated best electrocatalytic activity for OER compared to the other synthesized catalysts at the same applied potential (1.6 V). On the other hand, the ZnGa1Al1O4 composition demonstrated excellent faradaic efficiency of ∼ 90% towards HER. From this work we can achieve multifunctional applications towards optoelectronics and electrocatalysis just by modulating Al/Ga ratio in ZnGa2-xAlxO4.

Synthesis and feasibility studies of doping U at Ti site of Y2Ti2O7 as a radioactive waste immobilization matrix.

In pursuit of clean and green nuclear energy one of the major challenges is to effectively immobilize the nuclear waste. In this context A2B2O7 type pyrochlore owing to its structural flexibility, ability to accommodate ions at both A/B-sites and high radiation tolerance has demonstrated excellent capability to store highly radioactive actinide ions. To fill the major gap area of actinide doping at the B site we have taken up the challenge of doping uranium ions at the Ti site of Y2Ti2O7 type pyrochlore. An yttria titanate (Y2Ti2-xUxO7; x = 0.05, 0.075, 0.1, 0.2, and 0.3) based matrix with uranium doped at the Ti site was synthesized using a simple gel combustion route under an air atmosphere. Rietveld refined X-ray diffraction (XRD) demonstrated that Y2Ti2O7 can accommodate U up to 5 mol% in the Ti site without any phase separation, which was further confirmed using Raman spectroscopy. Y2Ti2O7 based matrices are found to be radiation stable up to 1000 kGy and at the same time they are moderately thermally stable and on a par with the values reported for pyrochlores. Uranium in Y2Ti2O7 stabilizes in +6 oxidation state in the form of uranyl ion distributed near and far off from titanium vacancies with distinct excited state lifetime. This work could provide a smart and strategic way for selecting a suitable advanced ceramic matrix for immobilization of high level waste with additional and important information on solubility limit, actinide speciation, radiation/thermal stability, actinide concentration, etc.

Ample Lewis Acidic Sites in Mg2B2O5 Facilitate N2 Electroreduction through Bonding-Antibonding Interactions.

Extensive research on the electrochemical nitrogen reduction reaction (NRR) has put forward a sound list of potential catalyst materials with properties inducing N2 adsorption, protonation, and reduction. However, rather than a random selection of catalysts, it is essential to understand the vitals in terms of orbital orientation and charge distribution that actually manipulate the rate-determining steps of NRR. Realizing these factors, herein we have explored a main group earth-abundant Mg-based electrocatalyst Mg2B2O5 for NRR due to the abundance of Lewis acid sites in the catalyst favoring the bonding-antibonding interactions with the N2 molecules. Positron annihilation studies indicate that the electronic charge distribution within the catalyst has shallow surface oxygen vacancies. These features in the catalyst enabled a sound Faradaic efficiency of 46.4% at -0.1 V vs reversible hydrogen electrode for the selective NH3 production in neutral electrolyte. In situ Fourier transform infrared suggests a maximum N-N bond polarization at -0.1 V and detected H-N-H and -NH2 intermediates during the course of the NRR on the catalyst surface. In a broader picture, the biocompatibility of Mg2+ diversifies the utility of this catalyst material in N2/biofuel cell applications that would certainly offer a green alternative toward our goal of a sustainable society.

Stabilization of Eu2+ in Li2B4O7 with the BO3 network through U6+ co-doping and defect engineering.

Owing to the unique 4f-5d transitions and the involvement of 5d electrons, the divalent europium (Eu2+) ion is extensively used as a dopant ion in luminescent materials for phosphor-converted light emitting diodes (pc-LEDs) and other technological applications. Earlier reports in most of the cases have shown that the reduction of Eu3+ to Eu2+ requires very high temperatures and large hydrogen flux. In this study, a co-doping strategy with higher valent U6+ ions was utilized to successfully stabilize Eu2+ ions in the Li2B4O7 (LTB) host with both the BO3 and BO4 network in low H2 flux of only 8%. It is postulated that charge transfer occurs from U to Eu, resulting in the reduction of the charged state of Eu and the reaction probably proceeds via the formation of paramagnetic transient [U5+-Eu3+] species in the co-doped LTB. The same is also believed to be facilitated by the enhanced formation of Li-O type vacancy clusters in co-doped samples and enhanced oxygen vacancies in a reducing atmosphere. We believe this work will pave a new pathway for stabilizing the unusual oxidation state of lanthanides and transition metal ions through co-doping with hexavalent uranium ions.

Metal Oxide Nanomaterials: From Fundamentals to Applications.

This Special Issue of Nanomaterials, "Metal Oxide Nanomaterials: From Fundamentals to Applications", highlights the development and understanding of different types of metal oxide nanoparticles and their use for applications in luminescence, photocatalysis, water-oil separation, optoelectronics, gas sensors, energy-saving smart windows, etc [...].

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.

Design of need-based phosphors and scintillators by compositional modulation in the ZnGa2-xAlxO4:Cr3+ spinel: pure compound versus solid solutions.

Materials that can depict persistent deep red light under both ultraviolet (UV) and X-ray illumination can be a boon to sustainable economy, particularly for optical imaging, solid state lighting, and anticounterfeiting applications. Herein, we have made a series of compounds starting from ZnGa2O4:Cr3+ to ZnAl2O4:Cr3+ (individual spinel) by substituting the varied concentration of Al3+ in place of Ga3+ in ZnGa2-xAlxO4:Cr3+ (solid solution). By virtue of the structural and defect engineering doping strategy, the photo and radioluminescence are expected to be improved. Both Cr and Al doping was found to be energetically favorable in ZnGa2O4, where the same does not hold true for Ga doping in ZnAl2O4, as indicated by the DFT-calculated defect formation energies. There seems to be ordering around the dopant ion in the solid solutions compared to either ZnGa2O4 or ZnAl2O4 and is also reflected to as lower persistent luminescence (PerL) lifetimes. PerL under UV, in general. was found to be lower with the enhancement in the Al3+ content endowed by the formation of Cr-Cr ion pair, lower probability of antisite formation, and widening band gap. On the other hand, X-ray excited emission enhances in the solid solution due to the decrease in cation inversion and associated defects. Confocal Microscopy showed that larger particles depicted much brighter deep red emission but failed to percolate to the human cells to a detectable limit; hence, future work is needed for the functionalization of the ZnGa2-xAlxO4:Cr3+ spinel. This work could be of great implication in designing need-based materials, where UV and X-ray excitation is required, for deep red emission with persistent characteristics from chromium-doped spinels.

Excitation-Dependent Photoluminescence of BaZrO3:Eu3+ Crystals.

The elucidation of local structure, excitation-dependent spectroscopy, and defect engineering in lanthanide ion-doped phosphors was a focal point of research. In this work, we have studied Eu3+-doped BaZrO3 (BZOE) submicron crystals that were synthesized by a molten salt method. The BZOE crystals show orange-red emission tunability under the host and dopant excitations at 279 nm and 395 nm, respectively, and the difference is determined in terms of the asymmetry ratio, Stark splitting, and intensity of the uncommon 5D0 → 7F0 transition. These distinct spectral features remain unaltered under different excitations for the BZOE crystals with Eu3+ concentrations of 0-10.0%. The 2.0% Eu3+-doped BZOE crystals display the best optical performance in terms of excitation/emission intensity, lifetime, and quantum yield. The X-ray absorption near the edge structure spectral data suggest europium, barium, and zirconium ions to be stabilized in +3, +2, and +4 oxidation states, respectively. The extended X-ray absorption fine structure spectral analysis confirms that, below 2.0% doping, the Eu3+ ions occupy the six-coordinated Zr4+ sites. This work gives complete information about the BZOE phosphor in terms of the dopant oxidation state, the local structure, the excitation-dependent photoluminescence (PL), the concentration-dependent PL, and the origin of PL. Such a complete photophysical analysis opens up a new pathway in perovskite research in the area of phosphors and scintillators with tunable properties.

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.