Metal ions in unusual valency states

Sellers, Robin M.

doi:10.1021/ed058p114

Cited by 7 publications

(5 citation statements)

References 34 publications

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“…This was interpreted as a strong evidence for O 2 – presence. Chromium and nickel did not react with 1,4-benzoquinone, suggesting that no O 2 – is formed. , Buxton et al favored a side-on complex structure for nickel …”

Section: Resultsmentioning

confidence: 99%

“…Chromium and nickel did not react with 1,4-benzoquinone, suggesting that no O 2 − is formed. 89,90 Buxton et al favored a side-on complex structure for nickel. 9 Mass spectrometry does not provide direct structural information, but indirect evidence can be obtained from a nanocalorimetric analysis of the reactivity data, 72,91 from isotopic labeling experiments, and from CID.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

et al. 2012

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The reactions of hydrated monovalent transition metal ions M(+)(H(2)O)(n), M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward molecular oxygen, nitrous oxide, and carbon dioxide were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Clusters containing monovalent chromium, cobalt, nickel, or zinc were reactive toward O(2), while only hydrated cobalt was reactive toward N(2)O. A strongly size dependent reactivity was observed. Chromium and cobalt react very slowly with carbon dioxide. Nanocalorimetric analysis, (18)O(2) exchange, and collision induced dissociation (CID) experiments were done to learn more about the structure of the O(2) products. The thermochemistry for cobalt, nickel, and zinc is comparable to the formation of O(2)(-) from hydrated electrons. These results suggest that cobalt, nickel, and zinc are forming M(2+)/O(2)(-) ion pairs in the cluster, while chromium rather forms a covalently bound dioxygen complex in large clusters, followed by an exothermic dioxide formation in clusters with n ≤ 5. The results show that hydrated singly charged transition metal ions exhibit highly specific reactivities toward O(2), N(2)O, and CO(2).

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

et al. 2012

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“…This difference in behavior is purely chemical in nature, reflecting the higher electronegativity of Zn and its tendency toward the covalent bond formation, which is further confirmed by its Bader charge being consistently less positive than the +2 formal charge (Table ). In fact, similar to Mg 2+ ion, the occurrence of metastable monovalent Zn + ion is an established topic with several reports and reviews. , …”

Section: Resultsmentioning

confidence: 99%

“…In fact, similar to Mg 2+ ion, the occurrence of metastable monovalent Zn + ion is an established topic with several reports and reviews. 59,60 It is postulated and generally accepted 61 that multielectron redox reactions follow through sequential elementary reactions (i.e., single-electron transfers) with different rate constants. However, our knowledge of solid-state diffusion of multivalent ions and the corresponding mechanisms for charge redistribution is still very limited.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Mass Transfer of Divalent Ions in an Oxide Host: Comparison of Mg²⁺ and Zn²⁺ Diffusion in Hexagonal K_xW₃O₉ Bronze

Asl

Manthiram

2019

Chem. Mater.

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Pure and isovalent cation-substituted potassium hexagonal tungsten bronze (KHTB) have been synthesized and used as a model oxide host to study the electrochemically driven bulk diffusion of divalent Mg 2+ and Zn 2+ ions. For the cation substitution, tungsten has been replaced by 10% Mo or 5% Cr as a strategy to mitigate the slow diffusivities of the divalent ions. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) studies reveal the superior kinetics of Zn 2+ insertion compared to that of Mg 2+ , majorly due to the sluggish desolvation/electroadsorption of Mg species at the electrode−electrolyte interface in an organohaloaluminate-based electrolyte. For both divalent cations, the insertion/extraction kinetics exhibits a profound improvement with the isovalent cation-substituted KHTB phases due to the synergistic effect of particle size reduction and enhanced ionic diffusivities. Hence, maximum insertion amounts of 0.18 and 0.20 mol, respectively, for Mg 2+ and Zn 2+ per (W 1−x M x ) 3 O 9 formula unit (M = Mo or Cr) have been achieved within the electrolyte stability window, whereas the unsubstituted KHTB is essentially inactive. Further EIS studies in symmetric cells indicated the inherently faster kinetics of Zn 2+ diffusion compared to that of Mg 2+ in identical hosts. Calculations based on density functional theory (DFT) were implemented to probe the local atomic environment of the diffusing ions. The DFT study suggests that the Zn-ion transition state is stabilized by ∼0.4 eV compared to that of Mg 2+ through a host-to-guest charge transfer, a consequence of the tendency of Zn 2+ ions to form covalent bonds compared to Mg 2+ with the oxide anion.

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“…In turn, this causes unbound free-Ni 2+ to localize at the charged negative groups, leading to an increase in the thickness of the stain with time in the membranes. By blanking the beam, deexcitation of this dynamic process leads to expulsion of excess Ni 2+ ions. ,,− The effects of beam-induced radiolysis and osmotic pressure are discussed further in the Supporting Information Sections XIII and XVI. ,,− …”

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confidence: 99%

In Situ Ni²⁺ Stain for Liposome Imaging by Liquid-Cell Transmission Electron Microscopy

et al. 2020

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Solvated soft matter, both biological and synthetic, can now be imaged in liquids using liquid-cell transmission electron microscopy (LCTEM). However, such systems are usually composed solely of organic molecules (low Z elements) producing low contrast in TEM, especially within thick liquid films. We aimed to visualize liposomes by LCTEM rather than requiring cryogenic TEM (cryoTEM). This is achieved here by imaging in the presence of aqueous metal salt solutions. The increase in scattering cross-section by the cation gives a staining effect that develops in situ, which could be captured by real space TEM and verified by in situ energy dispersive x-ray spectroscopy (EDS). We identified beam-induced staining as a time-dependent process that enhances contrast to otherwise low contrast materials. We describe the development of this imaging method and identify conditions leading to exceptionally low electron doses for morphology visualization of unilamellar vesicles before beam-induced damage propagates.

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Metal ions in unusual valency states

Abstract: This paper is concerned with the formation of novel valency states, their characterization and chemical behavior.

Cited by 7 publications

References 34 publications

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Mass Transfer of Divalent Ions in an Oxide Host: Comparison of Mg²⁺ and Zn²⁺ Diffusion in Hexagonal K_xW₃O₉ Bronze

In Situ Ni²⁺ Stain for Liposome Imaging by Liquid-Cell Transmission Electron Microscopy

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Metal ions in unusual valency states

Abstract: This paper is concerned with the formation of novel valency states, their characterization and chemical behavior.

Cited by 7 publications

References 34 publications

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M+(H2O)n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M+(H2O)n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Mass Transfer of Divalent Ions in an Oxide Host: Comparison of Mg2+ and Zn2+ Diffusion in Hexagonal KxW3O9 Bronze

In Situ Ni2+ Stain for Liposome Imaging by Liquid-Cell Transmission Electron Microscopy

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Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Mass Transfer of Divalent Ions in an Oxide Host: Comparison of Mg²⁺ and Zn²⁺ Diffusion in Hexagonal K_xW₃O₉ Bronze

In Situ Ni²⁺ Stain for Liposome Imaging by Liquid-Cell Transmission Electron Microscopy