Elucidating the Lithiation Process in Fe3-δO4 Nanoparticles by Correlating Magnetic and Structural Properties.

Due to their high potential energy storage, magnetite (Fe3O4) nanoparticles have become appealing as anode materials in lithium-ion batteries. However, the details of the lithiation process are still not completely understood. Here, we investigate chemical lithiation in 70 nm cubic-shaped magnetite nanoparticles with varying degrees of lithiation, x = 0, 0.5, 1, and 1.5. The induced changes in the structural and magnetic properties were investigated using X-ray techniques along with electron microscopy and magnetic measurements. The results indicate that a structural transformation from spinel to rock salt phase occurs above a critical limit for the lithium concentration (xc), which is determined to be between 0.5< xc ≤ 1 for Fe3-δO4. Diffraction and magnetization measurements clearly show the formation of the antiferromagnetic LiFeO2 phase. Upon lithiation, magnetization measurements reveal an exchange bias in the hysteresis loops with an asymmetry, which can be attributed to the formation of mosaic-like LiFeO2 subdomains. The combined characterization techniques enabled us to unambiguously identify the phases and their distributions involved in the lithiation process. Correlating magnetic and structural properties opens the path to increasing the understanding of the processes involved in a variety of nonmagnetic applications of magnetic materials.

Probing spin waves in Co3O4 nanoparticles for magnonics applications.

The magnetic properties of spinel nanoparticles can be controlled by synthesizing particles of a specific shape and size. The synthesized nanorods, nanodots and cubic nanoparticles have different crystal planes selectively exposed on the surface. The surface effects on the static magnetic properties are well documented, while their influence on spin waves dispersion is still being debated. Our ability to manipulate spin waves using surface and defect engineering in magnetic nanoparticles is the key to designing magnonic devices. We synthesized cubic and spherical nanoparticles of a classical antiferromagnetic material Co3O4 to study the shape and size effects on their static and dynamic magnetic proprieties. Using a combination of experimental methods, we probed the magnetic and crystal structures of our samples and directly measured spin wave dispersions using inelastic neutron scattering. We found a weak, but unquestionable, increase in exchange interactions for the cubic nanoparticles as compared to spherical nanoparticle and bulk powder reference samples. Interestingly, the exchange interactions in spherical nanoparticles have bulk-like properties, despite a ferromagnetic contribution from canted surface spins.

Environmental DNA: The First Snapshot of the Vertebrate Biodiversity in Three Sicilian Lakes.

Freshwater ecosystems play a key role in global diversity and are subject to a series of anthropic impacts, often leading to biodiversity loss. The organisms inhabiting these sites continuously release DNA into the environment through cells, excrement, gametes and/or decomposing matter; thus, evaluation of this eDNA could revolutionize the monitoring of biodiversity. In this study, environmental DNA metabarcoding was used for the first time in three Sicilian lakes: Lake Poma, Piana degli Albanesi Lake and Lake Scanzano. Results obtained provide the first snapshot of vertebrate biodiversity in these three lakes, where little is known, to provide valuable information useful for creating a baseline of knowledge regarding the biodiversity in these three lakes. Another important result was the detection of marine species, most likely due to some kind of anthropogenic contamination. Environmental DNA is a useful tool to evaluate both biodiversity and the ecological status of the environment; it has the potential to complement traditional methods, and the use of both approaches may offer a more comprehensive understanding of the ecosystem.

Biological Matrices from Cairina moschata as Non-Destructive Biomonitoring Tools to Study Environmental Quality of Urban and Extra-Urban Areas: A Case Study of Palermo (Sicily, Italy).

Biomonitoring is the qualitative observation and the measurement of biosphere parameters aimed at modelling the environment, evaluating its quality, and studying the effects of alterations on different ecological levels. In this work, trace metal concentrations were assessed using non-destructive biomonitoring tools as blood and feathers of the allochthonous aquatic bird Cairina moschata, collected within two areas of the Palermo metropolitan area, Sicily, differently exposed to air pollution: Parco D'Orleans, in a central urban location, and Monreale, southwest of the city centre. Higher concentrations in both blood and feathers collected in Parco D' Orleans were found for lead, tin and selenium, but the same was not observed for other metals. The concentrations were not above physiological tolerance in any case. The comparison between blood and feathers allowed to realize that the latter are more useful for biomonitoring analyses, as they are indicative of both external contamination and bioaccumulation. Treatment with nitric acid highlighted that the feathers collected in Parco D' Orleans had higher metal bioaccumulation than the ones collected in Monreale; however, the treatment needs standardization. The present study confirms that feathers and blood from C. moschata are a convenient and non-destructive sampling tool for metal contamination analysis.

Perspectives on Iron Oxide-Based Materials with Carbon as Anodes for Li- and K-Ion Batteries.

The necessity for large scale and sustainable energy storage systems is increasing. Lithium-ion batteries have been extensively utilized over the past decades for a range of applications including electronic devices and electric vehicles due to their distinguishing characteristics. Nevertheless, their massive deployment can be questionable due to use of critical materials as well as limited lithium resources and growing costs of extraction. One of the emerging alternative candidates is potassium-ion battery technology due to potassium's extensive reserves along with its physical and chemical properties similar to lithium. The challenge to develop anode materials with good rate capability, stability and high safety yet remains. Iron oxides are potentially promising anodes for both battery systems due to their high theoretical capacity, low cost and abundant reserves, which aligns with the targets of large-scale application and limited environmental footprint. However, they present relevant limitations such as low electronic conductivity, significant volume changes and inadequate energy efficiency. In this review, we discuss some recent design strategies of iron oxide-based materials for both electrochemical systems and highlight the relationships of their structure performance in nanostructured anodes. Finally, we outline challenges and opportunities for these materials for possible development of KIBs as a complementary technology to LIBs.

Aging and Charge Compensation Effects of the Rechargeable Aqueous Zinc/Copper Hexacyanoferrate Battery Elucidated Using In Situ X-ray Techniques.

The zinc/copper hexacyanoferrate (Zn/CuHCF) cell has gained attention as an aqueous rechargeable zinc-ion battery (ZIB) owing to its open framework, excellent rate capability, and high safety. However, both the Zn anode and the CuHCF cathode show unavoidable signs of aging during cycling, though the underlying mechanisms have remained somewhat ambiguous. Here, we present an in-depth study of the CuHCF cathode by employing various X-ray spectroscopic techniques. This allows us to distinguish between structure-related aging effects and charge compensation processes associated with electroactive metal centers upon Zn2+ ion insertion/deinsertion. By combining high-angle annular dark-field-scanning electron transmission microscopy, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy, and elemental analysis, we reconstruct the picture of both the bulk and the surface. First, we identify a set of previously debated X-ray diffraction peaks appearing at early stages of cycling (below 200 cycles) in CuHCF. Our data suggest that these peaks are unrelated to hypothetical ZnxCu1-xHCF phases or to oxidic phases, but are caused by partial intercalation of ZnSO4 into graphitic carbon. We further conclude that Cu is the unstable species during aging, whose dissolution is significant at the surface of the CuHCF particles. This triggers Zn2+ ions to enter newly formed Cu vacancies, in addition to native Fe vacancies already present in the bulk, which causes a reduction of nearby metal sites. This is distinct from the charge compensation process where both the Cu2+/Cu+ and Fe3+/Fe2+ redox couples participate throughout the bulk. By tracking the K-edge fluorescence using operando XAS coupled with cyclic voltammetry, we successfully link the aging effect to the activation of the Fe3+/Fe2+ redox couple as a consequence of Cu dissolution. This explains the progressive increase in the voltage of the charge/discharge plateaus upon repeated cycling. We also find that SO42- anions reversibly insert into CuHCF during charge. Our work clarifies several intriguing structural and redox-mediated aging mechanisms in the CuHCF cathode and pinpoints parameters that correlate with the performance, which will hold importance for the development of future Prussian blue analogue-type cathodes for aqueous rechargeable ZIBs.

Monitoring Campaign over an Edible Dormouse Population (Glis glis; Rodentia: Gliridae) in Sicily: First Report of Mesocestodiasis.

This study reports on the health status of the edible dormouse (Glis glis) living in Nebrodi Park (Sicily, Italy), responsible for nut crop damage in the area. In the frame of a monitoring campaign for potential zoonotic risk involving 30 dormice, rectal and conjunctival swabs and fur and nest content were collected for bacteriological and parasitological examinations, respectively. A large presence of fleas belonging to Monopsyllus sciurorum was found. Necropsy of a dead dormouse revealed an infection of Mesocestoides lineatus, whose cysts were found in the abdomen cavity and on the liver; this is the first report of this in this species. Further studies are necessary to identify their role in the environment, considering the limited knowledge of this species in Italy.

Genetic admixture despite ecological segregation in a North African sparrow hybrid zone (Aves, Passeriformes, Passer domesticus × Passer hispaniolensis).

Under different environmental conditions, hybridization between the same species might result in different patterns of genetic admixture. Particularly, species pairs with large distribution ranges and long evolutionary history may have experienced several independent hybridization events over time in different zones of overlap. In birds, the diverse hybrid populations of the house sparrow (Passer domesticus) and the Spanish sparrow (Passer hispaniolensis) provide a striking example. Throughout their range of sympatry, these two species do not regularly interbreed; however, a stabilized hybrid form (Passer italiae) exists on the Italian Peninsula and on several Mediterranean islands. The spatial distribution pattern on the Eurasian continent strongly contrasts the situation in North Africa, where house sparrows and Spanish sparrows occur in close vicinity of phenotypically intermediate populations across a broad mosaic hybrid zone. In this study, we investigate patterns of divergence and admixture among the two parental species, stabilized and nonstabilized hybrid populations in Italy and Algeria based on a mitochondrial marker, a sex chromosomal marker, and 12 microsatellite loci. In Algeria, despite strong spatial and temporal separation of urban early-breeding house sparrows and hybrids and rural late-breeding Spanish sparrows, we found strong genetic admixture of mitochondrial and nuclear markers across all study populations and phenotypes. That pattern of admixture in the North African hybrid zone is strikingly different from i) the Iberian area of sympatry where we observed only weak asymmetrical introgression of Spanish sparrow nuclear alleles into local house sparrow populations and ii) the very homogenous Italian sparrow population where the mitogenome of one parent (P. domesticus) and the Z-chromosomal marker of the other parent (P. hispaniolensis) are fixed. The North African sparrow hybrids provide a further example of enhanced hybridization along with recent urbanization and anthropogenic land-use changes in a mosaic landscape.

Interfacial Reaction Mechanisms on Graphite Anodes for K-Ion Batteries.

Potassium-ion (K-ion) batteries (KIBs) potentially offer numerous advantages over conventional lithium-ion batteries as a result of the high natural abundance of potassium and its lower positive charge density compared with lithium. This introduces the possibility of using K-ion in fast charging applications, in which cost effectiveness is also a major factor. Unlike in sodium-ion batteries, graphite can be used as an anode in K-ion cells, for which an extensive supply chain, electrode manufacturing infrastructure, and knowledge already exist. However, the performance of graphite anodes in K-ion cells does not meet expectations, with rapid capacity fading and poor first cycle irreversible capacities often reported. Here, we investigate the formation and composition of the solid electrolyte interphase (SEI) as well as K+ insertion in graphite anodes in KIBs. Through the use of energy-tuned synchrotron-based X-ray photoelectron spectroscopy, we make a detailed analysis at three probing depths up to ∼50 nm of graphite anodes cycled to various potentials on the first discharge-charge cycle. Extensive SEI formation from a KPF6/DEC/EC electrolyte system is found to occur at low potentials during the insertion of potassium ions into graphite. During the subsequent removal of potassium ions from the structure, the thick SEI is partially stripped from the electrode, demonstrating that the SEI layer is unstable and contributes to a significant proportion of the capacity upon both discharge and charge. With this in mind, further work is required to develop an electrolyte system with stable SEI layer formation on graphite in order to advance the KIB technology.

Efficient BiVO4 Photoanodes by Postsynthetic Treatment: Remarkable Improvements in Photoelectrochemical Performance from Facile Borate Modification.

Water-splitting photoanodes based on semiconductor materials typically require a dopant in the structure and co-catalysts on the surface to overcome the problems of charge recombination and high catalytic barrier. Unlike these conventional strategies, a simple treatment is reported that involves soaking a sample of pristine BiVO4 in a borate buffer solution. This modifies the catalytic local environment of BiVO4 by the introduction of a borate moiety at the molecular level. The self-anchored borate plays the role of a passivator in reducing the surface charge recombination as well as that of a ligand in modifying the catalytic site to facilitate faster water oxidation. The modified BiVO4 photoanode, without typical doping or catalyst modification, achieved a photocurrent density of 3.5 mA cm-2 at 1.23 V and a cathodically shifted onset potential of 250 mV. This work provides an extremely simple method to improve the intrinsic photoelectrochemical performance of BiVO4 photoanodes.

Mitochondrial heteroplasmy in an avian hybrid form (Passer italiae: Aves, Passeriformes).

Mitochondrial heteroplasmy is the result from biparental transmission of mitochondrial DNA (mtDNA) to the offspring. In such rare cases, maternal and paternal mtDNA is present in the same individual. Though recent studies suggested that mtDNA heteroplasmy might be more common than previously anticipated, that phenomenon is still poorly documented and was mostly detected in case studies on hybrid populations. The Italian sparrow, Passer italiae is a homoploid hybrid form that occurs all across the Italian Peninsula mostly under strict absence of either of its parent species, the house sparrow (P. domesticus) and the Spanish sparrow (P. hispaniolensis). In this study, we document a new case of mitochondrial heteroplasmy from two island populations of P. italiae (Ustica and Lipari). Our analysis was based on the mitochondrial NADH dehydrogenase subunit 2 (ND2) that allows for a clear distinction between mitochondrial lineages of the two parental species. We amplified and sequenced the mitochondrial ND2 gene with specifically designed primer combinations for each of the two parental species. In two of our study populations, a single individual carried two different ND2 haplotypes from each of the two parental lineages. These findings contribute to current knowledge on the still poorly documented phenomenon of paternal leakage in vertebrates.

Unlocking high capacities of graphite anodes for potassium-ion batteries.

Graphite is considered a promising candidate as the anode for potassium-ion batteries (KIBs). Here, we demonstrate a significant improvement in performance through the ball-milling of graphite. Electrochemical techniques show reversible K-intercalation into graphitic layers, with 65% capacity retention after 100 cycles from initial capacities and extended cycling beyond 200 cycles. Such an affinity of the graphite towards storage of K-ions is explained by means of SEM and Raman analyses. Graphite ball-milling results in a gentle mechanical exfoliation of the graphene layers and simultaneous defect formation, leading to enhanced electrochemical performance.

Electrocatalytic Water Oxidation Promoted by 3 D Nanoarchitectured Turbostratic δ-MnOx on Carbon Nanotubes.

The development of manganese-based water oxidation electrocatalysts is desirable for the production of solar fuels, as manganese is earth-abundant, inexpensive, non-toxic, and has been employed by the Photosystem II in nature for a billion years. Herein, we directly constructed a 3 D nanoarchitectured turbostratic δ-MnOx on carbon nanotube-modified nickel foam (MnOx /CNT/NF) by electrodeposition and a subsequent annealing process. The MnOx /CNT/NF electrode gives a benchmark catalytic current density (10 mA cm-2 ) at an overpotential (η) of 270 mV under alkaline conditions. A steady current density of 19 mA cm-2 is obtained during electrolysis at 1.53 V for 1.0 h. To the best of our knowledge, this work represents the most efficient manganese-oxide-based water oxidation electrode and demonstrates that manganese oxides, as a structural and functional model of oxygen-evolving complex (OEC) in Photosystem II, can also become comparable to those of most Ni- and Co-based catalysts.

Iron-Based Electrodes Meet Water-Based Preparation, Fluorine-Free Electrolyte and Binder: A Chance for More Sustainable Lithium-Ion Batteries?

Environmentally friendly and cost-effective Li-ion cells are fabricated with abundant, non-toxic LiFePO4 cathodes and iron oxide anodes. A water-soluble alginate binder is used to coat both electrodes to reduce the environmental footprint. The critical reactivity of LiPF6 -based electrolytes toward possible traces of H2 O in water-processed electrodes is overcome by using a lithium bis(oxalato)borate (LiBOB) salt. The absence of fluorine in the electrolyte and binder is a cornerstone for improved cell chemistry and results in stable battery operation. A dedicated approach to exploit conversion-type anodes more effectively is also disclosed. The issue of large voltage hysteresis upon conversion/de-conversion is circumvented by operating iron oxide in a deeply lithiated Fe/Li2 O form. Li-ion cells with energy efficiencies of up to 92 % are demonstrated if LiFePO4 is cycled versus such anodes prepared through a pre-lithiation procedure. These cells show an average energy efficiency of approximately 90.66 % and a mean Coulombic efficiency of approximately 99.65 % over 320 cycles at current densities of 0.1, 0.2 and 0.3 mA cm-2 . They retain nearly 100 % of their initial discharge capacity and provide an unmatched operation potential of approximately 2.85 V for this combination of active materials. No occurrence of Li plating was detected in three-electrode cells at charging rates of approximately 5C. Excellent rate capabilities of up to approximately 30C are achieved thanks to the exploitation of size effects from the small Fe nanoparticles and their reactive boundaries.

Surface Layer Evolution on Graphite During Electrochemical Sodium-tetraglyme Co-intercalation.

One obstacle in sodium ion batteries is the lack of suitable anode materials. As recently shown, the most common anode material of the state of the art lithium ion batteries, graphite, can be used for sodium ion storage as well, if ether-based electrolyte solvents are used. These solvents cointercalate with the sodium ions leading to the highly reversible formation of ternary graphite intercalation compounds (t-GIC). In order for the solvent cointercalation to work efficiently, it is expected that only a very thin surface layer forms during electrochemical cycling. In this article, we therefore present the first dedicated study of the surface layer evolution on t-GICs using soft X-ray photoelectron spectroscopy. This technique with its inherent high surface sensitivity and low probing depth is an ideal tool to study the underlying interfacial reactions during the sodiation and desodiation of graphite. In this report, we apply this approach to graphite composite electrodes cycled in Na half cells with a 1 M sodium bis(fluorosulfonyl)imide/tetraethylene glycol dimethyl ether (NaFSI/TEG-DME) electrolyte. We have found a surface layer on the cycled electrodes, mainly composed of salt decomposition products and hydrocarbons, in line with irreversible capacity losses observed in the electrochemical cycling. Although this surface layer does not seem to block cointercalation completely, it seems to affect its efficiency resulting in a low Coulombic efficiency of the studied battery system.

Structure Characterization and Properties of K-Containing Copper Hexacyanoferrate.

Copper hexacyanoferrate, Cu(II)[Fe(III)(CN)6]2/3·nH2O, was synthesized, and varied amounts of K(+) ions were inserted via reduction by K2S2O3 (aq). Ideally, the reaction can be written as Cu(II)[Fe(III)(CN)6]2/3·nH2O + 2x/3K(+) + 2x/3e(-) ↔ K2x/3Cu(II)[Fe(II)xFe(III)1-x(CN)6]2/3·nH2O. Infrared, Raman, and Mössbauer spectroscopy studies show that Fe(III) is continuously reduced to Fe(II) with increasing x, accompanied by a decrease of the a-axis of the cubic Fm3̅m unit cell. Elemental analysis of K by inductively coupled plasma shows that the insertion only begins when a significant fraction, ∼20% of the Fe(III), has already been reduced. Thermogravimetric analysis shows a fast exchange of water with ambient atmosphere and a total weight loss of ∼26 wt % upon heating to 180 °C, above which the structure starts to decompose. The crystal structures of Cu(II)[Fe(III)(CN)6]2/3·nH2O and K2/3Cu[Fe(CN)6]2/3·nH2O were refined using synchrotron X-ray powder diffraction data. In both, one-third of the Fe(CN)6 groups are vacant, and the octahedron around Cu(II) is completed by water molecules. In the two structures, difference Fourier maps reveal three additional zeolitic water sites (8c, 32f, and 48g) in the center of the cavities formed by the -Cu-N-C-Fe- framework. The K-containing compound shows an increased electron density at two of these sites (32f and 48g), indicating them to be the preferred positions for the K(+) ions.

Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES.

The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V).

Sustainable Materials for Sustainable Energy Storage: Organic Na Electrodes.

In this review, we summarize research efforts to realize Na-based organic materials for novel battery chemistries. Na is a more abundant element than Li, thereby contributing to less costly materials with limited to no geopolitical constraints while organic electrode materials harvested from biomass resources provide the possibility of achieving renewable battery components with low environmental impact during processing and recycling. Together, this can form the basis for truly sustainable electrochemical energy storage. We explore the efforts made on electrode materials of organic salts, primarily carbonyl compounds but also Schiff bases, unsaturated compounds, nitroxides and polymers. Moreover, sodiated carbonaceous materials derived from biomasses and waste products are surveyed. As a conclusion to the review, some shortcomings of the currently investigated materials are highlighted together with the major limitations for future development in this field. Finally, routes to move forward in this direction are suggested.

Electrochemical fabrication and characterization of Cu/Cu2O multi-layered micro and nanorods in Li-ion batteries.

Electrodes composed of freestanding nano- and microrods composed of stacked layers of copper and cuprous oxide have been fabricated using a straightforward one-step template-assisted pulsed galvanostatic electrodeposition approach. The approach provided precise control of the thickness of each individual layer of the high-aspect-ratio rods as was verified by SEM, EDS, XRD, TEM and EELS measurements. Rods with diameters of 80, 200 and 1000 nm were deposited and the influence of the template pore size on the structure and electrochemical performance of the conversion reaction based electrodes in lithium-ion batteries was investigated. The multi-layered Cu2O/Cu nano- and microrod electrodes exhibited a potential window of more than 2 V, which was ascribed to the presence of a distribution of Cu2O (and Cu, respectively) nanoparticles with different sizes and redox potentials. As approximately the same areal capacity was obtained independent of the diameter of the multi-layered rods the results demonstrate the presence of an electroactive Cu2O layer with a thickness defined by the time domain of the measurements. It is also demonstrated that while the areal capacity of the electrodes decreased dramatically when the scan rate was increased from 0.1 to 2 mV s(-1), the capacity remained practically constant when the scan rate was further increased to 100 mV s(-1). This behaviour can be explained by assuming that the capacity is limited by the lithium ion diffusion rate though the Cu2O layer generated during the oxidation step. The electrochemical performance of present type of 3-D multi-layered rods provides new insights into the lithiation and delithiation reactions taking place for conversion reaction materials such as Cu2O.

Precursor-Less Coating of Nanoparticles in the Gas Phase.

This article introduces a continuous, gas-phase method for depositing thin metallic coatings onto (nano)particles using a type of physical vapor deposition (PVD) at ambient pressure and temperature. An aerosol of core particles is mixed with a metal vapor cloud formed by spark ablation by passing the aerosol through the spark zone using a hollow electrode configuration. The mixing process rapidly quenches the vapor, which condenses onto the core particles at a timescale of several tens of milliseconds in a manner that can be modeled as bimodal coagulation. Gold was deposited onto core nanoparticles consisting of silver or polystyrene latex, and silver was deposited onto gold nanoparticles. The coating morphology depends on the relative surface energies of the core and coating materials, similar to the growth mechanisms known for thin films: a coating made of a substance having a high surface energy typically results in a patchy coverage, while a coating material with a low surface energy will normally "wet" the surface of a core particle. The coated particles remain gas-borne, allowing further processing.