Ethylene carbonate adsorption on the major surfaces of lithium manganese oxide LiMnO spinel (0.000 < x < 0.375): a DFT+U-D3 study.

Understanding the surface reactivity of the commercial cathode material LiMnO towards the electrolyte is important to improve the cycling performance of secondary lithium-ion batteries and to prevent manganese dissolution. In this work, we have employed spin-polarized density functional theory calculations with on-site Coulomb interactions and long-range dispersion corrections [DFT+U-D3-(BJ)] to investigate the adsorption of the electrolyte component ethylene carbonate (EC) onto the (001), (011) and (111) surfaces of the fully lithiated and partially delithiated LiMnO spinel (0.000 < x < 0.

Electronic structure, ion diffusion and cation doping in the NaVO(PO) compound as a cathode material for Na-ion batteries.

Sodium-ion batteries are considered one of the most promising alternatives to lithium-ion batteries owing to the low cost and wide abundance of sodium. Phosphate compounds are promising materials for sodium-ion batteries because of their high structural stability, energy densities and capacities. Vanadium phosphates have shown high energy densities, but their sodium-ion diffusion and cation doping properties are not fully rationalized.

Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids.

The first members of a promising new family of hybrid amino acid-polyoxometalates have emerged from a search for modular functional molecules. Incorporation of glycine (Gly) or norleucine (Nle) ligands into an yttrium-tungstoarsenate structural backbone, followed by crystallization with p-methylbenzylammonium (p-MeBzNH3(+)) cations, affords (p-MeBzNH3)6K2(GlyH)[As(III)4(Y(III)W(VI)3)W(VI)44Y(III)4O159(Gly)8(H2O)14]⋅47 H2O (1) and enantiomorphs (p-MeBzNH3)15(NleH)3[As(III)4(Mo(V)2Mo(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11][As(III)4(Mo(VI)2W(VI)2)W(VI)44Y(III)4O160(Nle)9(H2O)11] (generically designated 2: L-Nle, 2 a; D-Nle, 2 b). An intensive structural, spectroscopic, electrochemical, magnetochemical and theoretical investigation has allowed the elucidation of site-selective metal substitution and photoreduction of the tetranuclear core of the hybrid polyanions.

Effect of electron (de)localization and pairing in the electrochemistry of polyoxometalates: study of Wells-Dawson molybdotungstophosphate derivatives.

Polyoxometalates (POMs) are inorganic entities featuring extensive and sometimes unusual redox properties. In this work, several experimental techniques as well as density functional theory (DFT) calculations have been applied to identify and assess the relevance of factors influencing the redox potentials of POMs. First, the position of the Mo substituent atom in the Wells-Dawson structure, α1- or α2-P2W17Mo, determines the potential of the first 1e(-) reduction wave.

99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers.

Electrochemical behavior of α1/α2-[Fe(H2O)P2W17O61](7-) isomers in solution: experimental and DFT studies.

The unusual redox behavior displayed by the two isomers of the Wells-Dawson phosphotungstate anion [Fe(H(2)O)P(2)W(17)O(61)](7-) is presented. The electrochemical measurements have been performed in aqueous media at different pH values from 0.5 up to 8.

Lanthanide polyoxocationic complexes: experimental and theoretical stability studies and Lewis acid catalysis.

The [ε-PMo(V)(8)Mo(VI)(4)O(36)(OH)(4){Ln(III)(H(2)O)}(4)](5+) (Ln=La, Ce, Nd, Sm) polyoxocations, called εLn(4), have been synthesized at room temperature as chloride salts soluble in water, MeOH, EtOH, and DMF. Rare-earth metals can be exchanged, and (31)P NMR spectroscopic studies have allowed a comparison of the affinity of the reduced {ε-PMo(12)} core, thus showing that the La(III) ions have the highest affinity and that rare earths heavier than Eu(III) do not react with the ε-Keggin polyoxometalate. DFT calculations provide a deeper insight into the geometries of the systems studied, thereby giving more accurate information on those compounds that suffer from disorder in crystalline form.