Nanofeather ruthenium nitride electrodes for electrochemical capacitors.

Fast charging is a critical concern for the next generation of electrochemical energy storage devices, driving extensive research on new electrode materials for electrochemical capacitors and micro-supercapacitors. Here we introduce a significant advance in producing thick ruthenium nitride pseudocapacitive films fabricated using a sputter deposition method. These films deliver over 0.

The rise of X-ray spectroscopies for unveiling the functional mechanisms in batteries.

Synchrotron-based techniques have been key tools in the discovery, understanding, and development of battery materials. In this review, some of the most suitable X-ray spectroscopy related techniques employed for addressing diverse scientific cases connected to battery science are highlighted. Furthermore, current shortcomings, intrinsic limitations, and ongoing challenges of individual techniques are pointed out, providing an outlook of future trends that are relevant to the battery research community.

Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox.

Anionic redox is a double-edged sword for Li-ion cathodes because it offers a transformational increase in energy density that is also negated by several detrimental drawbacks to its practical implementation. Among them, voltage hysteresis is the most troublesome because its origin is still unclear and under debate. Herein, we tackle this issue by designing a prototypical Li-rich cation-disordered rock-salt compound LiTiFeO that shows anionic redox activity and exceptionally large voltage hysteresis while exhibiting a partially reversible Fe migration between octahedral and tetrahedral sites.

Extending insertion electrochemistry to soluble layered halides with superconcentrated electrolytes.

Insertion compounds provide the fundamental basis of today's commercialized Li-ion batteries. Throughout history, intense research has focused on the design of stellar electrodes mainly relying on layered oxides or sulfides, and leaving aside the corresponding halides because of solubility issues. This is no longer true.

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides.

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure.

Elucidating the Origin of the Electrochemical Capacity in a Proton-Based Battery HIrO via Advanced Electrogravimetry.

Recently, because of sustainability issues dictated by societal demands, more importance has been given to aqueous systems and especially to proton-based batteries. However, the mechanisms behind the processes leading to energy storage in such systems are still not elucidated. Under this scope, our study is structured on the selection of a model electrode material, the protonic phase HIrO, and the scrutiny of the interfacial processes through suitable analytical tools.

Monitoring the Crystal Structure and the Electrochemical Properties of Na(VO)(PO)F through Fe Substitution.

We here present the synthesis of a new material, Na(VO)Fe(PO)F, by the sol-gel method. Its atomic and electronic structural descriptions are determined by a combination of several diffraction and spectroscopy techniques such as synchrotron X-ray powder diffraction and synchrotron X-ray absorption spectroscopy at V and Fe K edges, Fe Mössbauer, and P solid-state nuclear magnetic resonance spectroscopy. The crystal structure of this newly obtained phase is similar to that of Na(VO)(PO)F, with a random distribution of Fe ions over vanadium sites.

Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries.

Disordered rock salt cathodes showing both anionic and cationic redox are being extensively studied for their very high energy storage capacity. Mn-based disordered rock salt compounds show much higher energy efficiency compared to the Ni-based materials as a result of the different voltage hysteresis, 0.5 and 2 V, respectively.

Chemical Activity of the Peroxide/Oxide Redox Couple: Case Study of BaRuO in Aqueous and Organic Solvents.

The finding that triggering the redox activity of oxygen ions within the lattice of transition metal oxides can boost the performances of materials used in energy storage and conversion devices such as Li-ion batteries or oxygen evolution electrocatalysts has recently spurred intensive and innovative research in the field of energy. While experimental and theoretical efforts have been critical in understanding the role of oxygen nonbonding states in the redox activity of oxygen ions, a clear picture of the redox chemistry of the oxygen species formed upon this oxidation process is still missing. This can be, in part, explained by the complexity in stabilizing and studying these species once electrochemically formed.

Evidence for the natural origins of anomalously high chromium levels in soils of the Cecina Valley (Italy).

The problem of high levels of chromium is one of the most important issues in soils of the Mediterranean area, in particular those deriving from ophiolitic parent materials. Very often the chromium concentration is greater than the threshold values of legislation on soil pollution and the knowledge of the origin of contamination (natural or anthropogenic) is important to formulate risk characterization. This study evaluated the soils from three coastal areas of the Cecina Valley (Tuscany, Italy) to understand the origin of chromium in the soils, where high levels of hexavalent chromium were found in well and spring waters of the areas.

Nanocluster superstructures or nanoparticles? The self-consuming scaffold decides.

We show that using the same reaction procedure, by hindering or allowing the formation of a reaction intermediate, the Ag+dodecanethiolate polymeric complex, it is possible to selectively obtain Ag dodecanethiolate nanoparticles or Ag dodecanethiolate nanoclusters in the size range 4-2 nm. Moreover, the Ag dodecanethiolate nanoclusters display a lamellar superstructure templated from the precursor Ag+dodecanethiolate polymeric complex. A plausible formation mechanism is illustrated where, starting from the precursor and scaffold lamellar Ag+ thiolate polymeric complex, first the nanocluster Agn0 core is formed by reduction of isoplanar Ag+ ions, followed by Ag+ thiolate units that build protection, the nanocluster shell, around the core.

Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes.

Reversible anionic redox has rejuvenated the search for high-capacity lithium-ion battery cathodes. Real-world success necessitates the holistic mastering of this electrochemistry's kinetics, thermodynamics, and stability. Here we prove oxygen redox reactivity in the archetypical lithium- and manganese-rich layered cathodes through bulk-sensitive synchrotron-based spectroscopies, and elucidate their complete anionic/cationic charge-compensation mechanism.

Efficient artificial mineralization route to decontaminate Arsenic(III) polluted water - the Tooeleite Way.

Increasing exposure to arsenic (As) contaminated ground water is a great threat to humanity. Suitable technology for As immobilization and removal from water, especially for As(III) than As(V), is not available yet. However, it is known that As(III) is more toxic than As(V) and most groundwater aquifers, particularly the Gangetic basin in India, is alarmingly contaminated with it.

Microwave-assisted synthesis and electrochemical evaluation of VO2 (B) nanostructures.

Understanding how intercalation materials change during electrochemical operation is paramount to optimizing their behaviour and function and in situ characterization methods allow us to observe these changes without sample destruction. Here we first report the improved intercalation properties of bronze phase vanadium dioxide VO2 (B) prepared by a microwave-assisted route which exhibits a larger electrochemical capacity (232 mAh g(-1)) compared with VO2 (B) prepared by a solvothermal route (197 mAh g(-1)). These electrochemical differences have also been followed using in situ X-ray absorption spectroscopy allowing us to follow oxidation state changes as they occur during battery operation.

The effect of RE substitution in layered REO(0.5)F(0.5)BiS2: chemical pressure, local disorder and superconductivity.

We have studied the effect of RE substitution on the structure and the local atomic disorder in REO0.5F0.5BiS2 (RE = rare-earth) to understand their correlation with the bulk superconductivity in these materials.

Microscopic biomineralization processes and Zn bioavailability: a synchrotron-based investigation of Pistacia lentiscus L. roots.

Plants growing on polluted soils need to control the bioavailability of pollutants to reduce their toxicity. This study aims to reveal processes occurring at the soil-root interface of Pistacia lentiscus L. growing on the highly Zn-contaminated tailings of Campo Pisano mine (SW Sardinia, Italy), in order to shed light on possible mechanisms allowing for plant adaptation.

Microscopic processes ruling the bioavailability of Zn to roots of Euphorbia pithyusa L. pioneer plant.

Euphorbia pithyusa L. was used in a plant growth-promoting assisted field trial experiment. To unravel the microscopic processes at the interface, thin slices of E.

Local disorder investigation in NiS(2-x)Se(x) using Raman and Ni K-edge x-ray absorption spectroscopies.

We report on Raman and Ni K-edge x-ray absorption investigations of a NiS(2-x)Se(x) (with x = 0.00, 0.50/0.

Determination of local atomic displacements in CeO(1-x)F(x)BiS2 system.

We have used Bi and Ce L3-edges extended x-ray absorption fine structure measurements to study local structure of CeO(1-x)F(x)BiS2 system as a function of F-substitution. The local structure of both BiS2 active layer and CeO1-xFx spacer layer changes systematically. The in-plane Bi-S1 distance decreases (ΔRmax ∼ 0.

Temperature dependent nanoscale atomic correlations in Ir1-xPtxTe2 (x = 0.0, 0.03 and 0.04) system.

X-ray absorption near-edge structure (XANES) spectroscopy has been used to investigate the unoccupied electronic states and local geometry of Ir1-xPtxTe2(x = 0.0, 0.03 and 0.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles.

Spectromicroscopy of electronic phase separation in KxFe2-ySe2 superconductor.

Structural phase separation in AxFe2-ySe2 system has been studied by different experimental techniques, however, it should be important to know how the electronic uniformity is influenced, on which length scale the electronic phases coexist, and what is their spatial distribution. Here, we have used novel scanning photoelectron microscopy (SPEM) to study the electronic phase separation in KxFe2-ySe2, providing a direct measurement of the topological spatial distribution of the different electronic phases. The SPEM results reveal a peculiar interconnected conducting filamentary phase that is embedded in the insulating texture.