Cross-Investigation on Copper Nitroprusside: Combining XRD and XAS for In-Depth Structural Insights

The emerging energy demand and need to develop sustainable energy storage systems have drawn extensive attention to fundamental and applied research. Anion redox processes were proposed in cathodic materials in addition to traditional transition metal redox to boost the specific capacity and the electrochemical performance. Alternatively, copper nitroprusside (CuNP) features an electroactive nitrosyl ligand alongside the two structural metals (Fe, Cu), representing an alternative to anion redox in layered oxides. Here, a deep structural investigation is carried out on CuNP by complementing the long-range order sensitivity of X-ray diffraction (XRD) and the local atomic probe of X-ray absorption (XAS). Two different CuNP materials are studied, the hydrated and dehydrated forms. A new phase for hydrated CuNP not reported in the literature is solved, and Rietveld refined. The XAS spectra of the two materials at the Cu and Fe K-edges show a similar yet different atomic environment. The extended XAS spectra (EXAFS) analysis is accomplished by considering three- and four-body terms due to the high collinearity of the atomic chains and gives accurate insight into the first-, second-, and third-shell interatomic distances. Both materials are mounted in Li-ion and Na-ion cells to explore the link between structure and electrochemical performance. As revealed by the charge/discharge cycles, the cyclability in Na-ion cells is negatively affected by interstitial water. The similarity in the local environment and the electrochemical differences suggest a long-range structural dependence on the electrochemical performance.

Revisiting polyanionic LiFePO4 battery material for electric vehicles

Although oxide cathodes have been widely used in these Li-ion batteries, these cathodes suffer from instability of the oxygen close-packed structure. In contrast, polyanionic phosphates such as LiFePO4 have incredible lattice stability and safety features owing to the strong covalent bond of P-O, which constrains the oxygen atoms and minimizes the defects of the oxygen site, resulting in stable frameworks. In addition, the presence of the strong P-O covalent bond stabilizes the anti-bonding transitional metal redox couple through an M-O-P inductive effect to generate a relatively high potential. Hence, polyanionic LiFePO4 has been an ideal choice of cathode materials for batteries deployed in electric vehicles. In this review, we revisit the basic features and development of LiFePO4, as an attempt to speeding its future deployment in massive electric vehicles.

Bacteria-induced mineral precipitation: a mechanistic review

Micro-organisms contribute to Earth’s mineral deposits through a process known as bacteria-induced mineral precipitation (BIMP). It is a complex phenomenon that can occur as a result of a variety of physiological activities that influence the supersaturation state and nucleation catalysis of mineral precipitation in the environment. There is a good understanding of BIMP induced by bacterial metabolism through the control of metal redox states and enzyme-mediated reactions such as ureolysis. However, other forms of BIMP often cannot be attributed to a single pathway but rather appear to be a passive result of bacterial activity, where minerals form as a result of metabolic by-products and surface interactions within the surrounding environment. BIMP from such processes has formed the basis of many new innovative biotechnologies, such as soil consolidation, heavy metal remediation, restoration of historic buildings and even self-healing concrete. However, these applications to date have primarily incorporated BIMP-capable bacteria sampled from the environment, while detailed investigations of the underpinning mechanisms have been lagging behind. This review covers our current mechanistic understanding of bacterial activities that indirectly influence BIMP and highlights the complexity and connectivity between the different cellular and metabolic processes involved. Ultimately, detailed insights will facilitate the rational design of application-specific BIMP technologies and deepen our understanding of how bacteria are shaping our world.

Sedimentary trace metals: improving proxies for deoxygenation in coastal European seas

<p>Deoxygenation in response to eutrophication and climate change in coastal systems is increasing worldwide. Low oxygen conditions cause the chemical transformation of redox-sensitive trace metals (e.g. molybdenum and uranium) in seawater, and their subsequent transport to the sediment. Sedimentary trace metal contents can therefore be used as a record of changes in bottom water oxygen conditions allowing the history of deoxygenation to be reconstructed. However, most trace metal studies have focused on strongly reducing and sulfidic settings, leaving mildly reducing and oxygenated (but eutrophic) settings vastly understudied. Currently, it is unknown to what extent existing trace metal redox proxies are applicable to reconstruct oxygen conditions in coastal zones experiencing mild deoxygenation, despite the fact that such areas occupy vast stretches of the coastal oceans. Here, we study trace metal enrichments in 13 European coastal marine sites with varying bottom water redox conditions and depositional environments. Our data demonstrates that sedimentary molybdenum and uranium contents are sensitive to deoxygenation across a range of settings, although the mechanisms of enrichment may vary. Improved understanding of molybdenum and uranium dynamics in mildly reducing coastal settings will facilitate the development of reliable and widely applicable molybdenum and uranium-based redox proxies.</p>