SAUR63 stimulates cell growth at the plasma membrane.

In plants, regulated cell expansion determines organ size and shape. Several members of the family of redundantly acting Small Auxin Up RNA (SAUR) proteins can stimulate plasma membrane (PM) H+-ATPase proton pumping activity by inhibiting PM-associated PP2C.D phosphatases, thereby increasing the PM electrochemical potential, acidifying the apoplast, and stimulating cell expansion. Similarly, Arabidopsis thaliana SAUR63 was able to increase growth of various organs, antagonize PP2C.D5 phosphatase, and increase H+-ATPase activity. Using a gain-of-function approach to bypass genetic redundancy, we dissected structural requirements for SAUR63 growth-promoting activity. The divergent N-terminal domain of SAUR63 has a predicted basic amphipathic α-helix and was able to drive partial PM association. Deletion of the N-terminal domain decreased PM association of a SAUR63 fusion protein, as well as decreasing protein level and eliminating growth-promoting activity. Conversely, forced PM association restored ability to promote H+-ATPase activity and cell expansion, indicating that SAUR63 is active when PM-associated. Lipid binding assays and perturbations of PM lipid composition indicate that the N-terminal domain can interact with PM anionic lipids. Mutations in the conserved SAUR domain also reduced PM association in root cells. Thus, both the N-terminal domain and the SAUR domain may cooperatively mediate the SAUR63 PM association required to promote growth.

Enhancing P2/O3 Biphasic Cathode Performance for Sodium-Ion Batteries: A Metaheuristic Approach to Multi-Element Doping Design.

Sodium-ion batteries (SIBs) have emerged as a compelling alternative to lithium-ion batteries (LIBs), exhibiting comparable electrochemical performance while capitalizing on the abundant availability of sodium resources. In SIBs, P2/O3 biphasic cathodes, despite their high energy, require furthur improvements in stability to meet current energy demands. This study introduces a systematic methodology that leverages the meta-heuristically assisted NSGA-II algorithm to optimize multi-element doping in electrode materials, aiming to transcend conventional trial-and-error methods and enhance cathode capacity by the synergistic integration of P2 and O3 phases. A comprehensive phase analysis of the meta-heuristically designed cathode material Na0.76Ni0.20Mn0.42Fe0.30Mg0.04Ti0.015Zr0.025O2 (D-NFMO) is presented, showcasing its remarkable initial reversible capacity of 175.5 mAh g-1 and exceptional long-term cyclic stability in sodium cells. The investigation of structural composition and the stabilizing mechanisms is performed through the integration of multiple characterization techniques. Remarkably, the irreversible phase transition of P2→OP4 in D-NFMO is observed to be dramatically suppressed, leading to a substantial enhancement in cycling stability. The comparison with the pristine cathode (P-NFMO) offers profound insights into the long-term electrochemical stability of D-NFMO, highlighting its potential as a high-voltage cathode material utilizing abundant earth elements in SIBs. This study opens up new possibilities for future advancements in sodium-ion battery technology.

Heterosynaptic Plasticity in a Vertical Two-Terminal Synaptic Device.

Vertical two-terminal synaptic devices based on resistive switching have shown great potential for emulating biological signal processing and implementing artificial intelligence learning circuitries. To mimic heterosynaptic behaviors in vertical two-terminal synaptic devices, an additional terminal is required for neuromodulator activity. However, adding an extra terminal, such as a gate of the field-effect transistor, may lead to low scalability. In this study, a vertical two-terminal Pt/bilayer Sr1.8Ag0.2Nb3O10 (SANO) nanosheet/Nb:SrTiO3 (Nb:STO) device emulates heterosynaptic plasticity by controlling the number of trap sites in the SANO nanosheet via modulation of the tunneling current. Similar to biological neuromodulation, we modulated the synaptic plasticity, pulsed pair facilitation, and cutoff frequency of a simple two-terminal device. Therefore, our synaptic device can add high-level learning such as associative learning to a neuromorphic system with a simple cross-bar array structure.

Dynamic Changes of an Anodized FeNi Alloy during the Oxygen Evolution Reaction under Alkaline Conditions.

An efficient and durable oxygen evolution reaction (OER) catalyst is necessary for the water-splitting process toward energy conversion. The OER through water oxidation reactions could provide electrons for H2O, CO2, and N2 reduction and produce valuable compounds. Herein, the FeNi (1:1 Ni/Fe) alloy as foam, after anodizing at 50 V in a two-electrode system in KOH solution (1.0 M), was characterized by Raman spectroscopy, diffuse reflectance spectroscopy (DRS), X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), transmission electron microscopy (TEM), high-angle annular dark-field imaging (HAADF)-scanning transmission electron microscopy (STEM) and used as an efficient and durable OER electrocatalyst in KOH solution (1.0 M). The overpotential for the onset of the OER based on extrapolation of the Tafel plot was 225 mV. The overpotentials for the current densities of 10 and 30 mA/cm2 are observed at 270 and 290 mV, respectively. In addition, a low Tafel slope is observed, 38.0 mV per decade, for the OER. To investigate the mechanism of the OER, in situ surface-enhanced Raman spectroscopy was used to detect FeNi hydroxide and characteristic peaks of H2O. Impurities in KOH can adsorb onto the electrode surface during the OER. Peaks corresponding to Ni(III) (hydr)oxide and FeO42- can be detected during the OER, but high-valent FeNi (hydr)oxides are unstable and reduce under the open circle potential. Metal hydroxide transformations during the OER and anion adsorption should be carefully considered. In addition, Fe3O4 may convert to γ-Fe2O3 during the OER. This study aims to offer logical perspectives on the dynamic changes that occur during the OER under alkaline conditions in an anodized FeNi alloy. These changes encompass variations in morphology, surface oxidation, the generation of high-valent species, and phase conversion during the OER.

Lead in the Presence of Iron under Alkaline Conditions for the Oxygen-Evolution Reaction.

The oxygen-evolution reaction (OER) is a bottleneck in water splitting, which is a critical process for energy storage. In this study, the electrochemistry of Pb in the absence or presence of K2FeO4, as a soluble Fe source, is examined at pH ≈ 13. Our findings indicate that Pb exhibits limited catalytic activity for the OER under alkaline conditions. However, upon the addition of K2FeO4 to the electrolyte, a significant enhancement in the OER activity is observed in the presence of Pb. A notable observation in this study is the formation of stable Fe(IV) species following the OER during chronoamperometry experiments conducted in an alkaline solution. In addition to in situ Raman and visible spectroscopies, the operated electrodes have been characterized by high-resolution transmission electron microscopy, scanning electron microscopy, electron spin resonance spectroscopy, X-ray diffraction, electrochemical methods, electron paramagnetic resonance, and X-ray absorption spectroscopy. Through our experimental investigations, it is consistently observed that the presence of Fe ions on the surface of Pb/PbOx serves as an effective catalyst for the OER. However, it is important to note that this heightened OER activity is only temporary due to the low adhesion of Fe ions on the surface of Pb/PbOx.

Water Oxidation by a Copper(II) Complex with 6,6'-Dihydroxy-2,2'-Bipyridine Ligand: Challenges and an Alternative Mechanism.

Recently, copper(II) complexes have been extensively investigated as oxygen-evolution reaction (OER) catalysts through a water-oxidation reaction. Herein, new findings regarding OER in the presence of a Cu(II) complex with 6,6'-dihydroxy-2,2'-bipyridine ligand are reported. Using scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, Raman spectroscopy, in situ visible microscopy, in situ visible spectroelectrochemistry, X-ray absorption spectroscopy, and electrochemistry, it is hypothesized that the film formed on the electrode's surface in the presence of this complex causes an appropriated matrix to produce Cu (hydr)oxide. The resulting Cu (hydr)oxide could be a candidate for OER catalysis. The formed film could form Cu (hydr)oxide and stabilize it. Thus, OER activity increases in the presence of this complex.

Reaction between Nickel Hydroxide and Cerium(IV) Ammonium Nitrate in Aqueous Solution.

Cerium(IV) ammonium nitrate (CAN) has been extensively used as a sacrificial oxidant to study water-oxidation catalysts (WOCs). Although nickel hydroxide has been extensively investigated as WOCs, the water-oxidation reaction (WOR) and mechanistic studies in the presence of CAN and nickel hydroxide were rarely performed. Herein, using in situ Raman spectroscopy, in situ X-ray absorption spectroscopy, and in situ electron paramagnetic resonance spectroscopy, WOR in the presence of CAN and ß-Ni(OH)2 was investigated. The proposed WOR mechanism involves the oxidation of ß-Ni(OH)2 by CAN, leading to the formation of γ-NiO(OH). γ-NiO(OH), in the presence of acidic conditions, evolves oxygen and is reduced to Ni(II). In other words, the role of ß-Ni(OH)2 is the storage of four oxidizing equivalents by CAN, and then a four-electron reaction could result in a WOR with low activation energy. ß-Ni(OH)2 in CAN at concentrations of 0.10 M shows WOR with a maximum turnover frequency and a turnover number (for 1000 s) of 5.5 × 10-5/s and 2.0 × 10-2 mol (O2)/mol(Ni), respectively. In contrast to ß-Ni(OH)2, Ni(OH2)62+ (aq) could not be oxidized to γ-NiO(OH). Indeed, Ni(OH2)62+ (aq) is the decomposition product of ß-Ni(OH)2/CAN.

Unveiling the Oxygen Evolution Mechanism with FeNi (Hydr)oxide under Neutral Conditions.

Large-scale solar-driven water splitting is a way to store energy, but it requires the development of practical and durable oxygen evolution reaction (OER) catalysts. The present paper aims to investigate the mechanism of the OER, local pH, high-valent metal ions, limitations, conversions, and details during the OER in the presence of FeNi foam using in situ surface-enhanced Raman spectroscopy. This research also explores the use of in situ surface-enhanced Raman spectroscopy for detecting species on foam surfaces during the OER. The acidic media around the electrode not only limit the process but also affect the phosphate ion protonation and overall catalysis effectiveness. The study proposes that FeNi hydroxides serve as true catalysts for OER under neutral conditions, rather than FeNi phosphates. However, phosphate species remain crucial for proton transfer and water molecule adsorption. Changes observed in pH at the open-circuit potential suggest new insights concerning the coordination of Ni(II) to phosphate ions under certain conditions. By extrapolating the Tafel plot, the overpotential for the onset of OER was determined to be 470 mV. Furthermore, the overpotentials for current densities of 1 and 5 mA/cm2 were 590 and 790 mV, respectively. These findings offer valuable insights into the advancement of the OER catalysts and our understanding of the underlying mechanism for efficient water splitting; both are crucial elements for the purpose of energy storage.

Sodium Cobalticarborane: A Promising Precatalyst for Oxygen Evolution Reaction.

Water splitting is a helpful way of converting renewable electricity into fuel. The oxygen evolution reaction (OER) is a slow reaction that provides low-cost electrons for water reduction reactions. Thus, finding an efficient, low-cost, stable, and environmentally friendly OER catalyst is critical for water splitting. Here, sodium cobalticarborane (1) is introduced as a promising precatalyst for forming an OER cobalt-based catalyst. The cobalt-based catalyst was characterized by several methods and is suggested to be Co(III) (hydr)oxide. Using fluorine-doped tin oxide, glassy carbon, platinum, and gold electrodes, the OER activity of the cobalt-based precatalyst was investigated. The overpotential for the onset of OER in the presence of 1 is 315 mV using fluorine-doped tin oxide electrodes. The onsets of OERs in the presence of 1 using gold, platinum, and glassy carbon electrodes in KOH solutions (1.0 M) turned out to be 275, 284, and 330 mV, respectively. The nanoparticles on the gold electrodes exhibit significant OER activity with a Tafel slope of 63.8 mV/decade and an overpotential at 541 mV for 50 mA/cm2. In the case of the glassy carbon electrodes, a Tafel slope of 109.9 mV/decade and an overpotential of 548 mV for 10 mA/cm2 is recorded for the catalyst. This paper outlines an interesting approach to synthesize cobalt oxide for OER through a slow decomposition of a precatalyst.

Further Insight into the Conversion of a Ni-Fe Metal-Organic Framework during Water-Oxidation Reaction.

Metal-organic frameworks (MOFs) are extensively investigated as catalysts in the oxygen-evolution reaction (OER). A Ni-Fe MOF with 2,5-dihydroxy terephthalate as a linker has been claimed to be among the most efficient catalysts for the oxygen-evolution reaction (OER) under alkaline conditions. Herein, the MOF stability under the OER was reinvestigated by electrochemical methods, X-ray diffraction, X-ray absorption spectroscopy, energy-dispersive spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy, nuclear magnetic resonance, operando visible spectroscopy, electrospray ionization mass spectroscopy, and Raman spectroscopy. The peaks corresponding to the carboxylate group are observed at 1420 and 1520 cm-1 using Raman spectroscopy. The peaks disappear after the reaction, suggesting the removal of the carboxylate group. A drop in carbon content but growth in oxygen content after the OER was detected by energy-dispersive spectra. This shows that after the OER, the surface of MOF is oxidized. SEM images also show deep restructures in the surface morphology of this Ni-Fe MOF after the OER. Nuclear magnetic resonance and electrospray ionization mass spectrometry show the decomposition of the linker in alkaline conditions and even in the absence of potential. These experimental data indicate that during the OER, the synthesized MOF transforms to a Fe-Ni-layered double hydroxide, and the formed metal oxide is a candidate for the OER catalysis. Generalization is not true; however, taken together, these findings suggest that the stability of Ni-Fe MOFs under harsh oxidation conditions should be reconsidered.

Surface-Textured Mixed-Metal-Oxide Nanocrystals as Efficient Catalysts for ROS Production and Biofilm Eradication.

Next-generation catalysts are urgently needed to tackle the global challenge of antimicrobial resistance. Existing antimicrobials cannot function in the complex and stressful chemical conditions found in biofilms, and as a result, they are unable to infiltrate, diffuse into, and eradicate the biofilm and its associated matrix. Here, we introduce mixed-FeCo-oxide-based surface-textured nanostructures (MTex) as highly efficient magneto-catalytic platforms. These systems can produce defensive ROS over a broad pH range and can effectively diffuse into the biofilm and kill the embedded bacteria. Because the nanostructures are magnetic, biofilm debris can be scraped out of the microchannels. The key antifouling efficacy of MTex originates from the unique surface topography that resembles that of a ploughed field. These are captured as stable textured intermediates during the oxidative annealing and solid-state conversion of ß-FeOOH nanocrystals. These nanoscale surfaces will advance progress toward developing a broad array of new enzyme-like properties at the nanobio interface.

Identification of Single-Atom Ni Site Active toward Electrochemical CO2 Conversion to CO.

Electrocatalytic conversion of CO2 into value-added products offers a new paradigm for a sustainable carbon economy. For active CO2 electrolysis, the single-atom Ni catalyst has been proposed as promising from experiments, but an idealized Ni-N4 site shows an unfavorable energetics from theory, leading to many debates on the chemical nature responsible for high activity. To resolve this conundrum, here we investigated CO2 electrolysis of Ni sites with well-defined coordination, tetraphenylporphyrin (N4-TPP) and 21-oxatetraphenylporphyrin (N3O-TPP). Advanced spectroscopic and computational studies revealed that the broken ligand-field symmetry is the key for active CO2 electrolysis, which subordinates an increase in the Ni redox potential yielding NiI. Along with their importance in activity, ligand-field symmetry and strength are directly related to the stability of the Ni center. This suggests the next quest for an activity-stability map in the domain of ligand-field strength, toward a rational ligand-field engineering of single-atom Ni catalysts for efficient CO2 electrolysis.

Novel synthetic 3'-untranslated regions for controlling transgene expression in transgenic Aedes aegypti mosquitoes.

Transgenic technology for mosquitoes is now more than two decades old, and a wide array of control sequences have been described for regulating gene expression in various life stages or specific tissues. Despite this, comparatively little attention has been paid to the development and validation of other transgene-regulating elements, especially 3'-untranslated regions (3'UTRs). As a consequence, the same regulatory sequences are often used multiple times in a single transgene array, potentially leading to instability of transgenic effector genes. To increase the repertoire of characterized 3'UTRs available for genetics-based mosquito control, we generated fifteen synthetic sequences based on the base composition of the widely used SV40 3'UTR sequence, and tested their ability to contribute to the expression of reporter genes EGFP or luciferase. Transient transfection in mosquito cells identified nine candidate 3'UTRs that conferred moderate to strong gene expression. Two of these were engineered into the mosquito genome through CRISPR/Cas9-mediated site-specific insertion and compared to the original SV40 3'UTR. Both synthetic 3'UTRs were shown to successfully promote transgene expression in all mosquito life stages (larva, pupa and adults), similar to the SV40 3'UTR, albeit with differences in intensity. Thus, the synthetic 3'UTR elements described here are suitable for regulating transgene expression in Ae. aegypti, and provide valuable alternatives in the design of multi-gene cassettes. Additionally, the synthetic-scramble approach we validate here could be used to generate additional functional 3'UTR elements in this or other organisms.

Uptake, Distribution, and Transformation of Zerovalent Iron Nanoparticles in the Edible Plant Cucumis sativus.

Here, we investigated the fate of nanoscale zerovalent iron (nZVI) on the Cucumis sativus under both hydroponic and soil conditions. Seedlings were exposed to 0, 250, and 1000 mg/L (or mg/kg soil) nZVI during 6-9 weeks of a growth period. Ionic controls were prepared using Fe-EDTA. None of the nZVI treatments affected the plant biomass. On the basis of the total iron contents and the superparamagnetic property of nZVI-exposed roots, there was no evidence of pristine nZVI translocation from the roots to shoots. Electron microscopy revealed that the transformed iron nanoparticles are stored in the root cell membrane and the vacuoles of the leaf parenchymal cells. X-ray absorption spectroscopy identified ferric citrate (41%) and iron (oxyhydr)oxides (59%) as the main transformed products in the roots. The shoot samples indicated a larger proportion of ferric citrate (60%) compared to iron (oxyhydr)oxides (40%). The 1.8-fold higher expression of the CsHA1 gene indicated that the plant-promoted transformation of nZVI was driven by protons released from the root layers. The current data provide a basis for two potential nZVI transformation pathways in Cucumis sativus: (1) interaction with low molecular weight organic acid ligands and (2) dissolution-precipitation of the mineral products.

Mechanistic insights into the interaction between energetic oxygen ions and nanosized ZnFe2O4: XAS-XMCD investigations.

The interactions of energetic ions with multi-cation compounds and their consequences in terms of changes in the local electronic structure, which may facilitate intriguing hybridization between O 2p and metal d orbitals and magnetic ordering, are the subject of debate and require a deep understanding of energy transfer processes and magnetic exchange mechanisms. In this study, nanocrystals of ZnFe2O4 were exposed to O7+ ions with an energy of 100 MeV to understand, qualitatively and quantitatively, the metal-ligand field interactions, cation migration and magnetic exchange interactions by employing X-ray absorption fine structure measurements and X-ray magnetic circular dichroism to get deeper mechanistic insights. Nanosized zinc ferrite nanoparticles (NPs) with a size of ∼16 nm synthesized in the cubic spinel phase exhibited deterioration of the crystalline phase when 100 MeV O7+ ions passed through them. However, the size of these NPs remained almost the same. The behaviour of crystal deterioration is associated with the confinement of heat in this interaction. The energy confined inside the nanoparticles promotes cation redistribution as well as the modification of the local electronic structure. Prior to this interaction, almost 42% of Zn2+ ions occupied AO4 tetrahedra; however, this value increased to 63% after the interaction. An inverse effect was observed for metal ion occupancies in BO6 octahedra. The L-edge spectra of Fe and Zn reveal that the spin and valence states of the metal ions were not affected by this interaction. This effect is also supported by K-edge measurements for Fe and Zn. The t2g/eg intensity ratio in the O K-edge spectra decreased after this interaction, which is associated with detachment of Zn2+ ions from the lattice. The extent of hybridization, as estimated from the ratio of the post-edge to the pre-edge region of the O K-edge spectra, decreased after this interaction. The metal-oxygen and metal-metal bond lengths were modified as a result of this interaction, as determined from extended X-ray absorption fine structure measurements. These measurements further support the observation of cation migration from AO4 tetrahedra to AO6 octahedra and vice versa. The Fe L-edge magnetic circular dichroism spectra indicate that Fe3+ ions occupying sites in AO4 tetrahedra and BO6 octahedra exhibited antiferromagnetic-like ordering prior to this interaction. The NPs that interacted with energetic O ions displayed a different kind of magnetic ordering.

A parthenogenesis gene of apomict origin elicits embryo formation from unfertilized eggs in a sexual plant.

Apomixis is a naturally occurring mode of asexual reproduction in flowering plants that results in seed formation without the involvement of meiosis or fertilization of the egg. Seeds formed on an apomictic plant contain offspring genetically identical to the maternal plant. Apomixis has significant potential for preserving hybrid vigor from one generation to the next in highly productive crop plant genotypes. Apomictic Pennisetum/Cenchrus species, members of the Poaceae (grass) family, reproduce by apospory. Apospory is characterized by apomeiosis, the formation of unreduced embryo sacs derived from nucellar cells of the ovary and, by parthenogenesis, the development of the unreduced egg into an embryo without fertilization. In Pennisetum squamulatum (L.) R.Br., apospory segregates as a single dominant locus, the apospory-specific genomic region (ASGR). In this study, we demonstrate that the PsASGR-BABY BOOM-like (PsASGR-BBML) gene is expressed in egg cells before fertilization and can induce parthenogenesis and the production of haploid offspring in transgenic sexual pearl millet. A reduction of PsASGR-BBML expression in apomictic F1 RNAi transgenic plants results in fewer visible parthenogenetic embryos and a reduction of embryo cell number compared with controls. Our results endorse a key role for PsASGR-BBML in parthenogenesis and a newly discovered role for a member of the BBM-like clade of APETALA 2 transcription factors. Induction of parthenogenesis by PsASGR-BBML will be valuable for installing parthenogenesis to synthesize apomixis in crops and will have further application for haploid induction to rapidly obtain homozygous lines for breeding.

Mechanistic insights on the electronic properties and electronic/atomic structure aspects in orthorhombic SrVO3 thin films: XANES-EXAFS study.

Correlations among the B-O6 octahedra distortions, existing polymorphous phases, band structures and electronic conductivities of ABO3 perovskites are matters for debate and require a deep understanding of their local atomic/electronic structures and diverse assets. In this study, to illustrate the distortion in V-O6 octahedra and its implication on the band structure and electronic properties, spectroscopic investigations on the RF-sputtering grown insulating SrVO3 thin films were employed using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). V K-edge and V L3,2-edge XANES, along with atomic multiplet calculations, have confirmed the 4+ oxidation state of V ions in the pristine and annealed SrVO3 thin films. Lower t2g/eg peak intensity ratio and smaller energy separation between t2g and eg peaks in the O K-edge XANES spectra, compared to the VO2 reference sample, have confirmed a larger V-O6 distortion in the orthorhombic SrVO3 thin films. Moreover, from the EXAFS data analysis, the local orthorhombic structure has been identified in the pristine and annealed SrVO3 thin films, compelling significant distortion in the V-O6 octahedra. Dimerization in the vanadium chains and V-V twisting, caused by V-O6 octahedra distortion, manifests a miscellaneous ligand field interaction between O 2p and V 3d orbitals and facilitates (i) a larger separation between the bonding and antibonding d‖ orbitals and (ii) an upward shift of the π* band in the band structure, leading to larger band gaps in the insulating SrVO3 thin films. Our spectroscopy results may open up new avenues for the mechanism of insulating/conducting character in other complicated perovskite materials using XANES-EXAFS.

Bifunctional Ce(1-x)Eu(x)O2 (0 ≤x≤ 0.3) nanoparticles for photoluminescence and photocatalyst applications: an X-ray absorption spectroscopy study.

Ce1-xEuxO2 (0 ≤x≤ 0.3) nanoparticles (NPs) were synthesized by the chemical precipitation method. The microstructures and morphology were characterized by synchrotron X-ray diffraction and high resolution transmission electron microscopy. X-ray absorption near edge structure (XANES) spectra at the Eu M5,4-edge and atomic-multiplet calculations revealed that Eu(3+) was predominantly present in the CeO2 lattice and Eu(2+) was negligibly present within the entire doping range. The detailed analysis of the Ce M5,4-edge and the O K-edge has shown strong dependence of the Ce(3+)/Ce(4+) ratio and oxygen vacancy with Eu content. Extended X-ray absorption fine structure (EXAFS) spectra at the Ce K-edge, along with theoretical fitting, have shown systematic variation in the coordination number, bond length and Debye-Waller factor with Eu doping. A blue shift in the absorption edge was observed which implies a net increase in the charge transfer gap between the O 2p and Ce 4f bands due to the increased number of Ce(3+) ions in the Eu doped samples. The excitation and emission spectra of pure CeO2 NPs did not show any photoluminescence (PL) characteristic; however, Ce1-xEuxO2 (x = 0.1-0.3) NPs showed significant improvements in the 4f-4f, (5)D0-(7)F2 and (5)D0-(7)F1 transitions induced luminescence properties. Eu doping has two major effects on the electronic structure and optical properties of CeO2 NPs: the first, at an Eu content of 10 mol%, is the formation of Ce(4+)-O-Eu(3+) networks, i.e., Eu(3+) ions substitute the Ce(4+) ions and introduce oxygen vacancies and Ce(3+) ions in the host lattice, which favors the (5)D0-(7)F2 induced PL properties. The other, at an Eu doping over 10 mol%, is the formation of both Ce(4+)-O-Eu(3+) and Ce(3+)-O-Eu(3+), i.e., Eu(3+) ions not only take substitutional sites of Ce(4+) ions but also replace a fraction of Ce(3+) ions in the CeO2 lattice which favors (5)D0-(7)F1 induced PL properties. As an application of CeO2 NPs towards the degradation of water pollutants, we demonstrated that the Ce1-xEuxO2 (0 ≤x≤ 0.3) NPs can serve as effective photocatalyst materials towards the degradation of the methyl-orange aqueous pollutant dye under UV light irradiation.

Electronic structure study of Ce1-xAxO2 (A = Zr & Hf) nanoparticles: NEXAFS and EXAFS investigations.

Single phase nanoparticles (NPs) of CeO2, Ce0.5Zr0.5O2, Ce0.5Hf0.5O2 and Ce0.5Hf0.25Zr0.25O2 were successfully synthesized by co-precipitation method at constant pH and temperature. The X-ray diffraction results revealed that the additive atoms did not segregate to form secondary phases but led to grain size variation in the NPs. The 10 Dq values in the near edge X-ray absorption fine structure (NEXAFS) spectra at the O K-edge did not vary in the same way as the average grain size was changed for the doped CeO2 NPs. The deconvolution of Ce M5-edge and detailed analysis of O K pre-edge peak have shown the higher Ce(+3)/(Ce(+3) + Ce(+4)) ratio in the Zr- and Hf-doped samples. The local atomic structure around the Ce, Zr and Hf atoms was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at Ce K-edge, Zr K-edge and Hf L3-edge, respectively, and the EXAFS data were fitted with the theoretical calculations. The 4f occupancy, Ce(+3)/(Ce(+3) + Ce(+4)) ratio of Ce ions, coordination number of Ce and Ce-Ce/Ce-O bond distances were sensitive to the additive atoms but not explicitly changed according to the grain size variation in the NPs.

Iron Integration in Nickel Hydroxide Matrix vs Surface for Oxygen-Evolution Reaction: Where the Nernst Equation Does Not Work.

This study focuses on the oxygen-evolution reaction (OER) activity comparison between two forms of NiFe (hydr)oxides: compound 1, where Fe ions are applied on the surface of nickel (hydr)oxide, and compound 2, with Fe ions incorporated into the structural matrix of nickel (hydr)oxide. The observed exponential link between Coulombic energy and the total charge of the system points to a direct proportionality between the potential and the concentration of oxidized nickel ions (e.g., V ∝ [oxidized Ni]), diverging from the logarithmic relationship outlined in the Nernst equation or its modifications, which is not evident in this case. Initial visible spectroscopy indicates a notable trend toward oxidation. As, during the oxidation, more Ni is oxidized, a repulsion effect develops, diminishing the likelihood of further oxidation, and a distinct linear correlation emerges between the quantity of oxidized Ni(II) and the applied potentials.