Browse
Submit Data
Databases
API
Help

Dataset Information

8 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Study of the Electronic Structure of Alkali Peroxides and Their Role in the Chemistry of Metal-Oxygen Batteries.

ABSTRACT: We use a multiconfigurational and correlated ab initio method to investigate the fundamental electronic properties of the peroxide MO₂^- (M = Li and Na) trimer to provide new insights into the rather complex chemistry of aprotic metal-O₂ batteries. These electrochemical systems are largely based on the electronic properties of superoxide and peroxide of alkali metals. The two compounds differ by stoichiometry: the superoxide is characterized by a M⁺O₂^- formula, while the peroxide is characterized by [M⁺]₂O₂^2-. We show here that both the peroxide and superoxide states necessarily coexist in the MO₂^- trimer and that they correspond to their different electronic states. The energetic prevalence of either one or the other and the range of their coexistence over a subset of the MO₂^- nuclear configurations is calculated and described via a high-level multiconfigurational approach.

SUBMITTER: Pierini A

PROVIDER: S-EPMC8558866 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes.

Project description:Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin-orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spin-orbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spin-orbit coupled states, and show measurement of UV···UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field.

| S-EPMC5187438 | biostudies-literature

THF-solvated Heavy Alkali Metal Benzyl Compounds (Na, Rb, Cs): Defined Deprotonation Reagents for Alkali Metal Mediation Chemistry.

Project description:The incorporation of heavy alkali metals into substrates is both challenging and essential for many reactions. Here, we report the formation of THF-solvated alkali metal benzyl compounds [PhCH2 M ⋅ (thf)n ] (M=Na, Rb, Cs). The synthesis was carried out by deprotonation of toluene with the bimetallic mixture n-butyllithium/alkali metal tert-butoxide and selective crystallization from THF of the defined benzyl compounds. Insights into the molecular structure in the solid as well as in solution state are gained by single crystal X-ray experiments and NMR spectroscopic studies. The compounds could be successfully used as alkali metal mediating reagents. The example of caesium showed the convenient use by deprotonating acidic C-H as well as N-H compounds to gain insight into the aminometalation using these reagents.

| S-EPMC9298144 | biostudies-literature

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.

Project description:Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe3 )(Dipp)]- (Dipp=2,6-iPr2 -C6 H3 ). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3 )(Dipp)}2 (μ-nBu)]∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.

| S-EPMC5096043 | biostudies-literature

Atomic-scale regulation of anionic and cationic migration in alkali metal batteries.

Project description:The regulation of anions and cations at the atomic scale is of great significance in membrane-based separation technologies. Ionic transport regulation techniques could also play a crucial role in developing high-performance alkali metal batteries such as alkali metal-sulfur and alkali metal-selenium batteries, which suffer from the non-uniform transport of alkali metal ions (e.g., Li+ or Na+) and detrimental shuttling effect of polysulfide/polyselenide anions. These drawbacks could cause unfavourable growth of alkali metal depositions at the metal electrode and irreversible consumption of cathode active materials, leading to capacity decay and short cycling life. Herein, we propose the use of a polypropylene separator coated with negatively charged Ti0.87O2 nanosheets with Ti atomic vacancies to tackle these issues. In particular, we demonstrate that the electrostatic interactions between the negatively charged Ti0.87O2 nanosheets and polysulfide/polyselenide anions reduce the shuttling effect. Moreover, the Ti0.87O2-coated separator regulates the migration of alkali ions ensuring a homogeneous ion flux and the Ti vacancies, acting as sub-nanometric pores, promote fast alkali-ion diffusion.

| S-EPMC8263716 | biostudies-literature

Proton enhanced dynamic battery chemistry for aprotic lithium-oxygen batteries.

Project description:Water contamination is generally considered to be detrimental to the performance of aprotic lithium-air batteries, whereas this view is challenged by recent contrasting observations. This has provoked a range of discussions on the role of water and its impact on batteries. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic lithium-oxygen batteries is revealed. Both lithium ions and protons are found to be involved in the oxygen reduction and evolution reactions, and lithium hydroperoxide and lithium hydroxide are identified as predominant discharge products. The crystallographic and spectroscopic characteristics of lithium hydroperoxide monohydrate are scrutinized both experimentally and theoretically. Intriguingly, the reaction of lithium hydroperoxide with triiodide exhibits a faster kinetics, which enables a considerably lower overpotential during the charging process. The battery chemistry unveiled in this mechanistic study could provide important insights into the understanding of nominally aprotic lithium-oxygen batteries and help to tackle the critical issues confronted.

| S-EPMC5303818 | biostudies-other

Metal peroxides for cancer treatment.

Project description:In recent years, metal peroxide (MO2) such as CaO2 has received more and more attention in cancer treatment. MO2 is readily decompose to release metal ions and hydrogen peroxide in the acidic tumor microenvironment (TME), resulting metal ions overloading, decreased acidity and elevated oxidative stress in TME. All of these changes making MO2 an excellent tumor therapeutic agent. Moreover, by combining MO2 with photosensitizers, enzymes or Fenton reagents, MO2 can assist and promote various tumor therapies such as photodynamic therapy and chemodynamic therapy. In this review, the synthesis and modification methods of MO2 are introduced, and the representative studies of MO2-based tumor monotherapy and combination therapy are discussed in detail. Finally, the current challenges and prospects of MO2 in the field of tumor therapy are emphasized to promote the development of MO2-based cancer treatment.

| S-EPMC7895646 | biostudies-literature

Non-equilibrium metal oxides via reconversion chemistry in lithium-ion batteries.

Project description:Binary metal oxides are attractive anode materials for lithium-ion batteries. Despite sustained effort into nanomaterials synthesis and understanding the initial discharge mechanism, the fundamental chemistry underpinning the charge and subsequent cycles-thus the reversible capacity-remains poorly understood. Here, we use in operando X-ray pair distribution function analysis combining with our recently developed analytical approach employing Metropolis Monte Carlo simulations and non-negative matrix factorisation to study the charge reaction thermodynamics of a series of Fe- and Mn-oxides. As opposed to the commonly believed conversion chemistry forming rocksalt FeO and MnO, we reveal the two oxide series topotactically transform into non-native body-centred cubic FeO and zincblende MnO via displacement-like reactions whose kinetics are governed by the mobility differences between displaced species. These renewed mechanistic insights suggest avenues for the future design of metal oxide materials as well as new material synthesis routes using electrochemically-assisted methods.

| S-EPMC7835223 | biostudies-literature

Phase Transfer-Mediated Degradation of Ether-Based Localized High-Concentration Electrolytes in Alkali Metal Batteries.

Project description:Localized high-concentration electrolytes (LHCEs) have attracted interest in alkali metal batteries due to the advantages of forming stable solid-electrolyte interphases (SEIs) on anodes and good chemical/electrochemical stability. Herein, a new degradation mechanism is revealed for ether-based LHCEs that questions their compatibility with alkali metal anodes (Li, Na, and K). Specifically, the ether solvent reacts with alkali metals to generate solvated electrons (es - ) that attack hydrofluoroether co-solvents to form a series of byproducts. The ether solvent essentially acts as a phase-transfer reagent that continuously transfers electrons from solid-phase metals into the solution phase, thus inhibiting the formation of stable SEI and leading to continuous alkali metal corrosion. Switching to an ester-based solvating solvent or intercalation anodes such as graphite or molybdenum disulfide has been shown to avoid such a degradation mechanism due to the absence of es - .

| S-EPMC9541886 | biostudies-literature

Interface chemistry of an amide electrolyte for highly reversible lithium metal batteries.

Project description:Metallic lithium is a promising anode to increase the energy density of rechargeable lithium batteries. Despite extensive efforts, detrimental reactivity of lithium metal with electrolytes and uncontrolled dendrite growth remain challenging interconnected issues hindering highly reversible Li-metal batteries. Herein, we report a rationally designed amide-based electrolyte based on the desired interface products. This amide electrolyte achieves a high average Coulombic efficiency during cycling, resulting in an outstanding capacity retention with a 3.5 mAh cm-2 high-mass-loaded LiNi0.8Co0.1Mn0.1O2 cathode. The interface reactions with the amide electrolyte lead to the predicted solid electrolyte interface species, having favorable properties such as high ionic conductivity and high stability. Operando monitoring the lithium spatial distribution reveals that the highly reversible behavior is related to denser deposition as well as top-down stripping, which decreases the formation of porous deposits and inactive lithium, providing new insights for the development of interface chemistries for metal batteries.

| S-EPMC7442789 | biostudies-literature

Diphenylacetylene stabilised alkali-metal nickelates: synthesis, structure and catalytic applications.

Project description:Whilst low-valent nickelates have recently been proposed as intermediates in Ni-catalysed reactions involving polar organometallics, their isolation and characterisation is often challenging due to their high sensitivity and reactivity. Advancing the synthetic, spectroscopic and structural insights of these heterobimetallic systems, here we report a new family of alkyne supported alkali-metal nickelates of the formula Li4(solv)n(Ar)4Ni2{μ2:η2,η2-Ph-CC-Ph} (where solv = Et2O, THF; Ar = Ph, o-Tol, naphthyl, 4-tBu-C6H4) which can be accessed through the combination of Ni(COD)2, Ph-CC-Ph and the relevant lithium aryl in a 2 : 1 : 4 ratio. Demonstrating the versatility of this approach, the sodium and potassium nickelates can also be accessed when using PhNa or via alkali-metal exchange with AMOtBu (AM = Na, K). When employing bulky or structurally constrained aryl-lithiums, mononickel complexes of the formula Li2(solv)n(Ar)2Ni{η2-Ph-CC-Ph} are instead obtained, highlighting the structural diversity of alkali-metal nickelates bearing alkyne ligands. Expanding the catalytic potential of these systems, their ability to promote the catalytic cyclotrimerisation of diphenylacetylene to hexaphenylbenzene was explored, with mononickel compounds bearing electron rich aryl-substituents displaying the best performance.

| S-EPMC9926332 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data