Coordination Structure Modulation in Group-VIB Metal Doped Ag3PO4 Augments Active Site Density for Electrocatalytic Conversion of N2 to NH3.

Doping is considered a promising material engineering strategy in electrochemical nitrogen reduction reaction (NRR), provided the role of the active site is rightly identified. This work concerns the doping of group VIB metal in Ag3PO4 to enhance the active site density, accompanied by d-p orbital mixing at the active site/N2 interface. Doping induces compressive strain in the Ag3PO4 lattice and inherently accompanies vacancy generation, the latter is quantified with positron annihilation lifetime studies (PALS). This eventually alters the metal d-electronic states relative to Fermi level and manipulate the active sites for NRR resulting into side-on N2 adsorption at the interface. The charge density deployment reveals Mo as the most efficient dopant, attaining a minimum NRR overpotential, as confirmed by the detailed kinetic study with the rotating ring disk electrode (RRDE) technique. In fact, the Pt ring of RRDE fails to detect N2H4, which is formed as a stable intermediate on the electrode surface, as identified from in-situ attenuated total reflectance-infrared (ATR-IR) spectroscopy. This advocates the complete conversion of N2 to NH3 on Mo/Ag3PO4-10 and the so-formed oxygen vacancies formed during doping act as proton scavengers suppressing hydrogen evolution reaction resulting into a Faradaic efficiency of 54.8% for NRR.

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.

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.

Nanoparticles can modulate network topological defects during multimodal elastomer formation.

We experimentally show that nanoparticles (NPs) can significantly regulate the network topological defects during a molecularly controlled elastomeric synthesis. Using positron annihilation lifetime spectroscopy, we demonstrate this on well-defined model systems of poly(dimethyl siloxane) elastomers and layered silicate nanoparticles (NPs). The evolutions of topological defects in elastomeric networks prepared from unimodal, bimodal, and NP dispersed bimodal elastomers are sequentially investigated. The extent of NP induced defect regulation is identified by varying the particle concentration from moderately low to an approximate upper limit. The fraction of free volume hole defects present between packed chains in the network generated by molecular control is significantly reduced. The fraction of smaller interstitial cavities near the cross-link sites shows a moderate increase at the lowest NP concentration. However, this fraction decreases at a high NP concentration and is nearly the same as that of bimodal networks that are devoid of NP infusion. Despite the variations in their fractions with NP infusion, the sizes of both these types of defects that remain in the network are minimally affected. The collective topological defects arising from chain induced heterogeneity also show a qualitative reduction upon NP infusion.

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.

One-pot hydrothermal preparation and defect-enhanced photocatalytic activity of Bi-doped CdWO4 nanostructures.

In the field of photocatalysis, the suppression of electron-hole recombination through various defects has been an emerging trend to enhance photocatalytic activity. The separation efficiency of electron-hole recombination of well-explored wolframite structured monoclinic CdWO4, prepared using the one-pot hydrothermal method, was further improved by Bi3+ doping in CdWO4. Studies using the partial density of states illustrated that Bi 6s and 6p orbitals altered the electronic band structure to the extent of lowering the band gap, resulting in more photon absorption. The positron annihilation lifetime studies unveiled the formation of cluster defects such as oxygen (V0o, Vo1+, Vo2+) along with cadmium vacancies () in Bi-doped CdWO4. The coexistence and synergy of more adsorption sites of V0o, Vo1+, Vo2+, VCd for dye and O2 molecules, suitable oxide/redox band potentials, the modified electronic band structure especially owing to W-O1-Bi-O2-W linkages, together with high surface area endowed Bi-doped CdWO4 to form ˙O2- radicals played a predominant role in the methyl orange degradation. All the experimental findings demonstrated conclusively that Bi3+ doping at Cd2+ facilitated CdWO4 to exhibit superior photocatalytic activity.

Deciphering the Role of Charge Compensator in Optical Properties of SrWO4:Eu3+:A (A = Li+, Na+, K+): Spectroscopic Insight Using Photoluminescence, Positron Annihilation, and X-ray Absorption.

Studies have been carried out to understand the specific role of the alkali charge compensator on the luminescence properties of an alkali ion (Li+, Na+, and K+) codoped SrWO4:Eu phosphor. The oxidation state of the europium ion was found to be +3 on the basis of X-ray absorption near edge structure (XANES) measurements. This is the first report of its kind where opposite effects of Li+ ion and Na+/K+ ions on photoluminescence intensity have been observed. Li+ ion codoping enhanced the photoluminescence intensity from SrWO4:Eu3+ phosphor while Na+/K+ ion codoping did not. On the other hand, the luminescence lifetime is maximum for the Na+ ion codoped sample and minimum for the Li+ ion codoped sample. The results could be explained successfully using time-resolved luminescence, positron annihilation lifetime spectroscopy (PALS), and extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Changes in the Eu-O bond length and Debye-Waller Factor (σ2) upon Li+/Na+/K+ codoping were monitored through EXAFS measurements. PALS also highlighted the fact that Li+ codoping is not contributing to reduction in the cation vacancies and might be occupying interstitial sites rather than lattice positions due to its very small size. On europium doping there is lowering in symmetry of SrO8 polyhedra from S4 to C6, which is reflected in an intense electric dipole transition in comparison to the magnetic dipole transition. This is also corroborated using trends in Judd-Ofelt parameters. The results have shown that the luminescence lifetime is better when the vacancy concentration is lower as induced by Na+ and K+ codoping, while the emission intensity is higher in the samples when distortion around Eu3+ is reduced as induced by Li+ codoping.

Characterizing the nanoclay induced constrained amorphous region in model segmented polyurethane-urea/clay nanocomposites and its implications on gas barrier properties.

There has been an increasing recognition of the fact that purely geometric factors associated with clay platelet dispersion in a polymer matrix cannot adequately explain the barrier properties of polymer/clay nanocomposites. The objective of the present work is to understand the nanoclay induced structural changes in a polyurethane-urea matrix and clay dispersion at different length scales using segment-specific characterization techniques and implications of the same in gas barrier properties using He, N2 and CO2 as probe molecules. Wide angle X-ray diffraction (WAXD) and positron annihilation life time spectroscopy (PALS) studies revealed nanoclay induced alterations in the chain packing of the amorphous soft segments of the polyurethane matrix at a molecular scale of a few Angstroms. The hard segment organization and the phase morphology of the nanocomposites, spanning length scales of several nanometers, were investigated by small angle X-ray scattering (SAXS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Furthermore, the presence of a constrained amorphous region surrounding the nanoclay was confirmed from AFM, WAXD and PALS results. Several pertinent structural variables from the gas transport point of view were deduced from these characterization techniques to understand the effect of the barrier properties in tandem with the clay dispersion morphology.

Solvent transport through hard-soft segmented polymer nanocomposites.

We conducted transport studies of a common solvent (toluene) in its condensed state, through a model hard-soft segmented polyurethane-clay nanocomposite. The solvent diffusivity is observed to be non-monotonic in a functional relationship with a filler volume fraction. In stark contrast, both classical tortuous path theory based geometric calculations and free volume measurements suggest the normally expected monotonic decrease in diffusivity with increase in clay volume fraction. Large deviations between experimentally observed diffusivity coefficients and those theoretically estimated from geometric theory are also observed. However, the equilibrium swelling of a nanocomposite as indicated by the solubility coefficient did not change. To gain an insight into the solvent interaction behavior, we conducted a pre- and post swollen segmented phase analysis of pure polymers and nanocomposites. We find that in a nanocomposite, the solvent has to interact with a filler altered hard-soft segmented morphology. In the altered phase separated morphology, the spatial distribution of thermodynamically segmented hard blocks in the continuous soft matrix becomes a strong function of filler concentration. Upon solvent interaction, this spatial distribution gets reoriented due to sorption and de-clustering. The results indicate strong non-barrier influences of nanoscale fillers dispersed in phase segmented block co-polymers, affecting solvent diffusivity through them. Based on pre- and post swollen morphological observations, we postulate a possible mechanism for the non-monotonic behaviour of solvent transport for hard-soft segmented co-polymers, in which the thermodynamic phase separation is influenced by the filler.

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.

Deciphering the bridge oxygen vacancy-induced cascading charge effect for electrochemical ammonia synthesis.

Oxygen vacancy engineering has recently been gaining much interest as the charging effect it induces in a material can be used for varied applications. Usually, semiconductor materials act poorly in electrocatalysis, particularly in the nitrogen reduction reaction (NRR), owing to their inherent charge deficit and huge band gap. Vacancy introduction can be a viable material engineering route to make use of these materials for the NRR. However, a detailed investigation of the vacancy-type and its role for the structural reorientation and charge redistribution of a material is lagging in the field of NRRs. This work thus focuses on the synthesis of oxygen vacancy-engineered SnO2 with a gradual structural transformation from in-plane (iov) to bridge-type oxygen vacancy (bov) density. Consequently, the electron occupancy of the sp3d hybrid orbital changes, leading to an upshifted valence band maxima towards the Fermi level. This has a profound effect on the nature of N2 adsorption and the extent of NN bond polarization. Sn atoms adjacent to the bov are found to have a fair density of dangling charges that accomplish the NRR process at a comparatively low overpotential and determine the binding strength of the intermediates on the active site. The obscured yet stable reaction intermediates are thereby identified with in situ ATR-IR studies. A restricted hydrogen evolution reaction Faradaic on the Sn-site (favored over O-atoms) results in a Faradaic efficiency of 48.5%, which is better than that reported in all the literature reports on SnO2 for the NRR. This study thus unveils sufficient insights into the role of oxygen vacancies in a crystal as well as electronic structural alteration of SnO2 and the effect of active sites on the rate kinetics of the NRR.

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.

Revealing the nano-level molecular packing in chitosan-NiO nanocomposite by using positron annihilation spectroscopy and small-angle X-ray scattering.

Chitosan-NiO nanocomposite (CNC) is shown to be a potential dielectric material with promising properties. CNCs containing NiO nanoparticles (0.2, 0.6, 1, 2, 5 wt %) are prepared through chemical methods. The inclusion of NiO nanoparticles in the chitosan matrix is confirmed by scanning electron microscopy (SEM) and X-ray diffraction. The morphology of the NiO nanoparticles and the nanocomposites is investigated by transmission electron microscopy and SEM, respectively. Positron annihilation lifetime spectroscopy (PALS) and the coincidence Doppler broadening (CDB) technique are used to quantify the free volume and molecular packing in the nanocomposites. The triplet-state positronium lifetime and the corresponding intensity show the changes in nanohole size, density, and size distribution as a function of NiO loading. Small-angle X-ray scattering indicates that the NiO aggregates are identical in all the CNCs. The momentum density distribution obtained from CDB measurements excludes the possibility of a contribution of vacant spaces (pores) available in NiO aggregates to the free volume of nanocomposites upon determination by using PALS. The results show systematic variation in free-volume properties and nano-level molecular packing as a function of NiO loading, which is presumed to play a vital role in determining the various properties of the nanocomposites.

Utilizing Energy Transfer in Mn2+/Ho3+/Yb3+ Tri-doped ZnAl2O4 Nanophosphors for Tunable Luminescence and Highly Sensitive Visual Cryogenic Thermometry.

Lanthanide (Ln3+)-doped upconversion (UC) phosphors converting near-infrared (NIR) light to visible light hold very high promise toward biomedical applications. The scientific findings on luminescent thermometers revealed their superiority for noninvasive thermal sensing. However, only few reports showcase their potential for applications in extreme conditions (temperatures below -70 °C) restricted by low thermal sensitivity. Here, we demonstrate the tailoring of luminescence properties via introducing Ho3+-Mn2+ energy transfer (ET) routes with judicious codoping of Mn2+ ions in ZnAl2O4/Ho3+,Yb3+ phosphor. Preferentially, a singular red UC emission is required to improve the bioimaging sensitivity and minimize tissue damage. We could attain UC emission with 94% red component by a two-photon UC process. Higher temperature annealing brings the color coordinates to the green domain, highlighting the potential for color-tunable luminescence switch. Moreover, this work investigates the thermometric properties of ZnAl2O4/Yb3+, Ho3+ in the range of 80-300 K and influence of inducing extra ET pathways by Mn2+ codoping. Interestingly, the luminescence intensities for nonthermally coupled (5F4,5S2) and the 5F5 radiative transitions of Ho3+ ions display opposite behavior at 80 and 300 K, which revealed competition between temperature-sensitive decay pathways. The codoping of Mn2+ ions is fruitful in causing a fourfold increase of absolute sensitivity. Notably, the color tunability from green through yellow to red is helpful in rough temperature estimation by naked eyes. The maximum relative (Sr) and absolute sensitivities (Sa) were estimated to be 1.89% K-1 (140 K) and 0.0734 K-1 (300 K), respectively. Even at 80 K, a Sa of 0.00447 K-1 and Sr of 0.6025% K-1 were achievable in our case, which are higher than most of the other Ln3+-based systems. The above-mentioned results demonstrate the potential of ZnAl2O4/Yb3+,Ho3+ for cryogenic optical thermometry and a strategy to design new Ln3+-based UC thermometers by taking advantage of ET routes.

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.

Modulated Ultrathin NiCo-LDH Nanosheet-Decorated Zr3+-Rich Defective NH2-UiO-66 Nanostructure for Efficient Photocatalytic Hydrogen Evolution.

Defect engineering through modification of their surface linkage is found to be an effective pathway to escalate the solar energy conversion efficiency of metal-organic frameworks (MOFs). Herein, defect engineering using controlled decarboxylation on the NH2-UiO-66 surface and integration of ultrathin NiCo-LDH nanosheets synergizes the hydrogen evolution reaction (HER) under a broad visible light regime. Diversified analytical methods including positron annihilation lifetime spectroscopy were employed to investigate the role of Zr3+-rich defects by analyzing the annihilation characteristics of positrons in NH2-UiO-66, which provides a deep insight into the effects of structural defects on the electronic properties. The progressively tuned photophysical properties of the NiCo-LDH@NH2-UiO-66-D-heterostructured nanocatalyst led to an impressive rate of HER (∼2458 µmol h-1 g-1), with an apparent quantum yield of ∼6.02%. The ultrathin NiCo-LDH nanosheet structure was found to be highly favored toward electrostatic self-assembly in the heterostructure for efficient charge separation. Coordination of Zr3+ on the surface of the NiCo-LDH nanosheet support through NH2-UiO-66 was confirmed by X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy techniques. Femtosecond transient absorption spectroscopy studies unveiled a photoexcited charge migration process from MOF to NiCo-LDH which favorably occurred on a picosecond time scale to boost the catalytic activity of the composite system. Furthermore, the experimental finding and HER activity are validated by density functional theory studies and evaluation of the free energy pathway which reveals the strong hydrogen binding over the surface and infers the anchoring effect of the ultrathin layered double hydroxide (LDH) in the vicinity of the Zr cluster with a strong host-guest interaction. This work provided a novel insight into efficient photocatalysis via defect engineering at the linker modulation in MOFs.

Investigation of nanoscopic free volume and interfacial interaction in an epoxy resin/modified clay nanocomposite using positron annihilation spectroscopy.

Epoxy/clay nanocomposites are synthesized using clay modified with the organic modifier N,N-dimethyl benzyl hydrogenated tallow quaternary ammonium salt (Cloisite 10A). The purpose is to investigate the influence of the clay concentration on the nanostructure, mainly on the free-volume properties and the interfacial interactions, of the epoxy/clay nanocomposite. Nanocomposites having 1, 3, 5 and 7.5 wt. % clay concentrations are prepared using the solvent-casting method. The dispersion of clay silicate layers and the morphologies of the fractured surfaces in the nanocomposites are studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The observed XRD patterns reveal an exfoliated clay structure in the nanocomposite with the lowest clay concentration (≤1 wt. %). The ortho-positronium lifetime (τ(3)), a measure of the free-volume size, as well as the fractional free volume (f(v)) are seen to decrease in the nanocomposites as compared to pristine epoxy. The intensity of free positron annihilation (I(2)), an index of the epoxy-clay interaction, decreases with the addition of clay (1 wt. %) but increases linearly at higher clay concentrations. Positron age-momentum correlation measurements are also carried out to elucidate the positron/positronium states in pristine epoxy and in the nanocomposites. The results suggest that in the case of the nanocomposite with the studied lowest clay concentration (1 wt. %), free positrons are primarily localized in the epoxy-clay interfaces, whereas at higher clay concentrations, annihilation takes place from the intercalated clay layers.

Harvesting Light from BaHfO3/Eu3+ through Ultraviolet, X-ray, and Heat Stimulation: An Optically Multifunctional Perovskite.

Materials with optical multifunctionality such as photoluminescence (PL), radioluminescence, and thermoluminescence (TL) are a boon for a sustainable society. BaHfO3 (barium hafnium oxide [BHO]) under UV irradiation demonstrated visible PL endowed by oxygen vacancies (OVs). Eu3+ doping in BHO (BHOE) introduces f-state impurity levels just below the conduction band for both Eu@Ba and Eu@Hf sites, causing efficient host-to-dopant energy transfer, generating intense 5D0 → 7F1 magnetic dipole transitions (MDT) with internal quantum yield of ∼70%. X-ray photoelectron spectroscopy and electron paramagnetic resonance showed the formation of OVs in both BHO and BHOE samples with more vacancies in the doped sample. The positron lifetime measurements suggested that Eu3+ ions are distributed at both Ba2+ and Hf4+ sites. The association of OVs with Hf4+ and Eu3+ ions due to high charge/radius ratio is considered to be responsible for lowering the symmetry around Eu3+ ions to C 4v in BHOE. Density functional theory studies of defect formation energy justified the same. Time-resolved emission spectroscopy showed distinct spectra for Eu@Ba and Eu@Hf sites corresponding to symmetric and asymmetric environments, respectively. This could be highly relevant in designing color tunable phosphor by forcing dopant ions at one specific site because Eu@Ba displayed orange emission whereas Eu@Hf displayed red emission. We could further harness BHOE for X-ray scintillator application by designing a thin film, which showed efficient conversion of high-energy X-ray into visible light. Under beta irradiation; both BHO and BHOE showed distinct TL glow curves as shallow traps were formed in the former and deep traps in the latter, which could have long-term implications in harnessing this material for persistent luminescence. We believe that BHO/BHOE demonstrated an extraordinary credential as a perovskite for multifunctional applications in the area of defect-induced light emission, UV phosphor, X-ray scintillator, and TL crystals.

α-ZrP Nanoreinforcement Overcomes the Trade-Off between Phosphoric Acid Dopability and Thermomechanical Properties: Nanocomposite HTPEM with Stable Fuel Cell Performance.

In recent times, high-temperature polymer electrolyte membranes (HTPEMs) have emerged as viable alternatives to the Nafion-based low-temperature-operated polymer electrolyte membrane fuel cells. This is owing to their higher tolerance to fuel impurities, efficient water management, and higher cathode kinetics. However, the most efficacious HTPEMs such as poly(benzimidazole) (PBI) or 2,5-poly(benzimidazole) (ABPBI), which rely on the extent of phosphoric acid (PA) doping level for fuel cell performance, suffer from poor mechanical properties at higher acid doping levels and dopant leaching during continuous operation. To overcome these issues, we report the synthesis of ABPBI membranes and fabrication of ABPBI-zirconium pyrophosphate (α-ZrP)-based nanocomposite membranes by an ex situ methodology using methane sulfonic acid as the solvent. The incorporation of hydrophilic α-ZrP into the membrane resulted in higher dopability of PA (6.5 mol) and proton conductivity (46 mS/cm) of the membranes (10 wt % of α-ZrP) as against the corresponding values of 3.6 mol and 27 mS/cm, respectively, for the pristine membrane. More remarkably, these property improvements could be achieved while simultaneously augmenting the thermomechanical properties and oxidative stability of the membranes. The unit-cell tests showed a marked improvement in the maximum power density for the nanocomposite membrane (335 mW/cm2 at 10 wt % α-ZrP content) over the pristine ABPBI membrane (200 mW/cm2). We also report for the first time the feasibility of a 100 W HTPEM fuel cell (HTPEMFC) stack operated with the nanocomposite membrane with an active area of 39 cm2. The HTPEMFC stack delivered a stable voltage and power output, with a voltage drop rate of 0.84 µV/h over a run time of 730 h.