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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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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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Iron speciation and coordination in lithium borate glasses.

Laurent Cormier1, Gérald Lelong1, Daniel R Neuville2

  • 1Sorbonne Université, Muséum National d'Histoire Naturelle, UMR CNRS 7590, IRD, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, IMPMC, cc115, 4 place Jussieu, 75005 Paris, France.

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This study shows iron in lithium borate glasses is primarily Fe3+. Increasing lithium oxide (Li2O) shifts the optical absorption edge and alters the borate network structure.

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Glass Science

Background:

  • Lithium borate glasses are versatile materials with tunable properties.
  • Understanding the role of transition metal ions like iron is crucial for developing new glass applications.
  • The coordination state and network interactions of iron in these glasses are not fully understood.

Purpose of the Study:

  • To investigate the influence of lithium oxide (Li2O) content and iron(III) oxide (Fe2O3) addition on lithium borate glasses.
  • To characterize the physical, optical, and structural properties of these modified glasses.
  • To determine the oxidation state and coordination environment of iron ions within the glass matrix.

Main Methods:

  • Optical absorption spectroscopy to analyze electronic transitions and absorption edge shifts.
  • X-ray absorption near edge structure (XANES) to identify iron oxidation states (Fe2+ vs. Fe3+).
  • X-ray absorption spectroscopy (XAS) to determine the coordination number and local environment of Fe3+ ions.
  • Raman spectroscopy to probe changes in the borate network structure and connectivity.

Main Results:

  • Iron exists predominantly as Fe3+ in the studied glasses, with minimal Fe2+ detected.
  • A blue shift in the optical absorption edge was observed with increasing Li2O content, linked to the transformation of BO3 to BO4 units.
  • Fe3+ ions were found to be primarily in tetrahedral coordination, with coordination numbers increasing at lower Li2O concentrations.
  • Raman spectroscopy indicated that Fe3+ disrupts the borate network, forming new linkages with boron atoms, especially in tetrahedral sites.

Conclusions:

  • The Li2O content significantly influences the structural evolution of lithium borate glasses, promoting the formation of BO4 units.
  • Iron, as Fe3+, integrates into the glass network, adopting tetrahedral coordination and affecting network connectivity.
  • The findings provide insights into the structure-property relationships of iron-doped lithium borate glasses, relevant for optical and material applications.