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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Tetrahedral Complexes
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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Hexagonal Mo Bronze: Single Crystal Structures, Electrocatalytic Hydrogen Evolution, and Proton Conductivity.

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Electrochemistry

Background:

  • Molybdenum trioxide (MoO3) is a versatile transition metal oxide with diverse applications.
  • Research has predominantly focused on the stable α-MoO3 polymorph.
  • Metastable polymorphs of MoO3 offer unique properties yet are less explored.

Purpose of the Study:

  • To synthesize and structurally characterize novel metastable hexagonal MoO3 single crystals.
  • To investigate the potential of these compounds as electrocatalysts for the hydrogen evolution reaction (HER).
  • To evaluate their performance as proton conductors.

Main Methods:

  • Single-crystal X-ray crystallography for comprehensive structural determination.
  • Synthesis of two metastable hexagonal MoO3 compounds: {Mn0.03Na0.01}@[Mo0.93VIMo0.07VO3] (1) and {Cu0.01Na0.01}@[Mo0.97VIMo0.03VO3] (2).
  • Electrochemical measurements for HER activity and proton conductivity assessment.

Main Results:

  • Compound 1 exhibited efficient HER electrocatalysis with an overpotential of 340 mV at 1 mA cm-2 and a Tafel slope of 75 mV/decade.
  • Compound 1 showed a high Faradaic efficiency of 88% and a turnover frequency of 2.9 s-1 for HER.
  • Compound 1 demonstrated significant proton conductivity (4.9 × 10-3 S cm-1 at 55 °C) via the Grotthuss mechanism with low activation energy (0.17 eV).

Conclusions:

  • Metastable hexagonal MoO3, specifically compound 1, presents promising catalytic and proton-conducting properties.
  • Compound 1 outperforms compound 2 in both HER electrocatalysis and proton conductivity.
  • The findings highlight the potential of exploring metastable MoO3 polymorphs for energy applications.