Green, Safe, and Reliable Synthesis of Bimetallic MOF-808 Nanozymes With Enhanced Aqueous Stability and Reactivity for Biological Applications.

Bimetallic metal-organic frameworks (MOFs) are promising nanomaterials whose reactivity towards biomolecules remains challenging due to issues related to synthesis, stability, control over metal oxidation state, phase purity, and atomic level characterization. Here, these shortcomings are rationally addressed through development of a synthesis of mixed metal Zr/Ce-MOFs in aqueous environment, overcoming significant hurdles in the development of MOF nanozymes, sufficiently stable on biologically relevant conditions. Specifically, a green and safe synthesis of Zr/Ce-MOF-808 is reported in water/acetic acid mixture which affords remarkably water-stable materials with reliable nanozymatic reactivity, including MOFs with a high Ce content previously reported to be unstable in water. The new materials outperform analogous bimetallic MOF nanozymes, showcasing that rational synthesis modifications could impart outstanding improvements. Further, atomic-level characterization by X-ray Absorption Fine Structure (XAFS) and X-ray Diffraction (XRD) confirmed superior nanozymes arise from differences in the synthetic method, which results in aqueous stable materials, and Ce incorporation, which perturbs the ligand exchange dynamics of the material, and could ultimately be used to fine tune the intrinsic MOF reactivity. Similar rational strategies which leverage metals in a synergistic manner should enable other water-stable bimetallic MOF nanozymes able to surpass existing ones, laying the path for varied biotechnological applications.

Enabling High-Stability of Aqueous-Processed Nickel-Rich Positive Electrodes in Lithium Metal Batteries.

Lithium batteries occupy the large-scale electric mobility market raising concerns about the environmental impact of cell production, especially regarding the use of poly(vinylidene difluoride) (teratogenic) and N-methyl-2-pyrrolidone (NMP, harmful). To avoid their use, an aqueous electrode processing route is utilized in which a water-soluble hybrid acrylic-fluoropolymer together with sodium carboxymethyl cellulose is used as binder, and a thin phosphate coating layer is in situ formed on the surface of the nickel-rich cathode during electrode processing. The resulting electrodes achieve a comparable performance to that of NMP-based electrodes in conventional organic carbonate-based electrolyte (LP30). Subsequently, an ionic liquid electrolyte (ILE) is employed to replace the organic electrolyte, building stable electrode/electrolyte interphases on the surface of the nickel-rich positive electrode (cathode) and metallic lithium negative electrode (anode). In such ILE, the aqueously processed electrodes achieve high cycling stability with a capacity retention of 91% after 1000 cycles (20 °C). In addition, a high capacity of more than 2.5 mAh cm-2 is achieved for high loading electrodes (≈15 mg cm-2 ) by using a modified ILE with 5% vinylene carbonate additive. A path to achieve environmentally friendly electrode manufacturing while maintaining their outstanding performance and structural integrity is demonstrated.

Structural Investigation of Quaternary Layered Oxides upon Na-Ion Deinsertion.

Na-ion batteries are emerging alternatives to Li-ion chemistries for large-scale energy storage applications. Quaternary layered oxide Na0.76Mn0.5Ni0.3Fe0.1Mg0.1O2 offers outstanding electrochemical performance in Na-ion batteries compared to pure-phase layered oxides because of the synergistic effect of the P/O-phase mixing. The material is indeed constituted by a mixture of P3, P2, and O3 phases, and a newly identified Na-free phase, i.e., nickel magnesium oxide phase, which improves heat removal and enhances the electrochemical performance. Herein, we structurally investigate, through synchrotron-radiation X-ray diffraction, the modifications occurring after full desodiation, detailing the material structural rearrangement upon Na removal and revealing the effect of two different charging protocols, i.e., constant current (CC) and constant current-constant voltage (CCCV). While the Na-free phase is electrochemically inactive, likely helping in homogenization of the thermal gradient in the electrode during cycling, O-P intergrown phases appear during the extraction of Na ions from interslab layers, and they are dependent on the desodiation level. The application of a constant voltage step at the end of the galvanostatic charge is responsible for a shortening of the interslab distance and a significant volume contraction (-11.9%).

Separation of terbium as a first step towards high purity terbium-161 for medical applications.

Terbium-161 is a medical radiolanthanide that has a beta decay energy and half-life similar to that of lutetium-177, which makes it a promising alternative for therapeutic purposes. The production route using an enriched gadolinium-160 target necessitates the purification of terbium-161 from the untransmuted target material as well as from its stable decay product, dysprosium-161. The separation of neighbouring lanthanides is challenging due to their similar chemical properties and prominent trivalent oxidation states. In this work, the aim is to change the oxidation state of terbium, resulting in the altering of chemical properties that ease the intragroup separation. To this end, a novel separation method is investigated, involving the electrochemical oxidation of terbium (3+) to terbium (4+) followed by anion exchange chromatography. The electrolysis conditions are set to the highest achievable conversion rate, followed by a dilution step during which the pH and electrolyte concentration are slightly lowered to obtain conditions that are compatible with the separation method. XAS analysis is done to characterize the carbonato complex of both oxidation states and to further elucidate the separation mechanism. The results show that the separation approach of combining electrochemical oxidation with anion exchange chromatography is promising for the purification of 161Tb for medical use.

Mapping Heterogeneity of Pristine and Aged Li- and Na-Mnhcf Cathode by Synchrotron-Based Energy-Dependent Full Field Transmission X-ray Microscopy.

Manganese hexacyanoferrate is a promising cathode material for lithium and sodium ion batteries, however, it suffers of capacity fading during the cycling process. To access the structural and functional characteristics at the nanometer scale, fresh and cycled electrodes are extracted and investigated by transmission soft X-ray microscopy, which allows chemical characterization with spatial resolution from position-dependent x-ray spectra at the Mn L-, Fe L- and N K-edges. Furthermore, soft X-rays prove to show superior sensitivity toward Fe, compare to hard X-rays. Inhomogeneities within the samples are identified, increasing in the aged electrodes, more dramatically in the Li-ion system, which explains the poorer cycle life as Li-ion cathode material. Local spectra, revealing different oxidation states over the sample with strong correlation between the Fe L-edge, Mn L-edge, and N K-edge, imply a coupling between redox centers and an electron delocalization over the host framework.

Influence of Vacancies in Manganese Hexacyanoferrate Cathode for Organic Na-Ion Batteries: A Structural Perspective.

Manganese hexacyanoferrates (MnHCF) are promising positive electrode materials for non-aqueous batteries, including Na-ion batteries, due to their large specific capacity (>130 mAh g-1 ), high discharge potential and sustainability. Typically, the electrochemical reaction of MnHCF associates with phase and structural changes, due to the Jahn-Teller (JT) distortion of Mn sites upon the charge process. To understand the effect of the MnHCF structure on its electrochemical performance, two MnHCF materials with different vacancies content are investigated herein. The electrochemical results show that the sample with lower vacancy content (4 %) exhibits relatively higher capacity retention of 99.1 % and 92.6 % at 2nd and 10th cycles, respectively, with respect to 97.4 % and 79.3 % in sample with higher vacancy content (11 %). Ex-situ X-ray absorption spectroscopy (XAS) and ex situ X-ray diffraction (XRD) characterization results show that a weaker cooperative JT-distortion effect and relatively smaller crystal structure modification occurred for the material with lower vacancies, which explains the better electrochemical performance in cycled electrodes.

Concentrated Electrolytes Enabling Stable Aqueous Ammonium-Ion Batteries.

Rechargeable aqueous batteries are promising devices for large-scale energy-storage applications because of their low-cost, inherent safety, and environmental friendliness. Among them, aqueous ammonium-ion (NH4 + ) batteries (AAIB) are currently emerging owing to the fast diffusion kinetics of NH4 + . Nevertheless, it is still a challenge to obtain stable AAIB with relatively high output potential, considering the instability of many electrode materials in an aqueous environment. Herein, a cell based on a concentrated (5.8 m) aqueous (NH4 )2 SO4 electrolyte, ammonium copper hexacyanoferrate (N-CuHCF) as the positive electrode (cathode), and 3,4,9,10-perylene-bis(dicarboximide) (PTCDI) as the negative electrode (anode) is reported. The solvation structure, electrochemical properties, as well as the electrode-electrolyte interface and interphase are systematically investigated by the combination of theoretical and experimental methods. The results indicate a remarkable cycling performance of the low-cost rocking-chair AAIB, which offers a capacity retention of ≈72% after 1000 cycles and an average output potential of ≈1.0 V.

Disclosing the Redox Pathway Behind the Excellent Performance of CuS in Solid-State Batteries.

Copper sulfide has attracted increasing attention as conversion-type cathode material for, especially, solid-state lithium-based batteries. However, the reaction mechanism behind its extraordinary electroactivity is not well understood, and the various explanations given by the scientific community are diverging. Herein, the CuS reaction dynamics are highlighted by examining the occurring redox processes via a cutting-edge methodology combining X-ray absorption fine structure spectroscopy, and chemometrics to overcome X-ray diffraction limitations posed by the poor material's crystallinity. The mathematical approach rules out the formation of intermediates and clarifies the direct conversion of CuS to Cu in a two-electron process during discharge and reversible oxidation upon delithiation. Two distinct voltage regions are identified corresponding to Cu- as well as the S-redox mechanisms occurring in the material.

Local Interactions Governing the Performances of Lithium- and Manganese-Rich Cathodes.

The local structural and electronical transformations occurring along the first charge and discharge cycle of Li- and Mn-rich Li[Li0.2Ni0.16Mn0.56Co0.08]O2 cathode material have been characterized by X-ray absorption spectroscopy at several complementary edges. The irreversible spinel formation, occurring at the expenses of the cycling layered phase during the first charge, is quantified (about 10%) and spatially localized. The local strains induced by the Ni oxidation have been evaluated. They induce the formation of a low spin Mn3+ in the layered structure in parallel to the irreversible formation of the spinel phase in the particles bulk. The charge balance has been quantified for all the elements along the first charging cycle, confirming a reversible oxygen oxidation along the charge. Overall, these quantitative results provide an experimental basis for modeling aimed to control the structure and its evolution, for instance, hindering the spinel formation for the benefit of the material cycle life.

Effect of Water and Alkali-Ion Content on the Structure of Manganese(II) Hexacyanoferrate(II) by a Joint Operando X-ray Absorption Spectroscopy and Chemometric Approach.

Manganese hexacyanoferrate (MnHCF) is made of earth-abundant elements by a safe and easy synthesis. The material features a higher specific capacity at a higher potential than other Prussian blue analogs. However, the effect of hydration is critical to determine the electrochemical performance as both the electrochemical behavior and the reaction dynamics are affected by interstitial/structural water and adsorbed water. In this study, the electrochemical activity of MnHCF is investigated by varying the interstitial ion content through a joint operando X-ray absorption spectroscopy and chemometric approach, with the intent to assess the structural and electronic modifications that occur during Na release and Li insertion, as well as the overall dynamic evolution of the system. In MnHCF, both the Fe and Mn centers are electrochemically active and undergo reversible oxidation during the interstitial ion extraction (Fe2+ /Fe3+ and Mn2+ /Mn3+ ). The adsorption of water results in irreversible capacity during charge but only on the Fe site, which is suggested by our chemometric analysis. The local environment of Mn experiences a substantial yet reversible Jahn-Teller effect upon interstitial ion removal because of the formation of trivalent Mn, which is associated with a decrease of the equatorial Mn-N bond lengths by 10 %.

Role of Manganese in Lithium- and Manganese-Rich Layered Oxides Cathodes.

Lithium-rich transition-metal-oxide cathodes are among the most promising materials for next generation lithium-ion-batteries because they operate at high voltages and deliver high capacities. However, their cycle-life remains limited, and individual roles of the transition-metals are still not fully understood. Using bulk-sensitive X-ray absorption and emission spectroscopy on Li[Li0.2Ni0.16Mn0.56Co0.08]O2, we inspect the behavior of Mn, generally considered inert upon the electrochemical process. During the first charge Mn appears to be redox-active showing a partial transformation from high-spin Mn4+ to Mn3+ in both high and low spin configurations, where the latter is expected to favor reversible cycling. The Mn redox-state with cycling continues changing in opposition to the expected charge compensation and is correlated with Ni oxidation/reduction, also spatially. The findings suggest that strain induced on the Mn-O sublattice by Ni oxidation triggers Mn reduction. These results unravel the Mn role in controlling the electrochemistry of Li-rich cathodes.