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Tungsten-niobium oxide bronzes: a bulk and surface structural study.

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Summary

Tungsten-niobium (W-Nb-O) oxide bronzes synthesized via hydrothermal methods show promise for various applications. Thermal treatments reveal structural changes, with Nb-rich materials stabilizing Lewis acid sites, enhancing glycerol dehydration reactions.

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Area of Science:

  • Materials Science
  • Solid-state Chemistry
  • Catalysis

Background:

  • Tungsten-niobium (W-Nb-O) oxide bronzes exhibit bronze-type crystal structures with significant functional properties.
  • These materials are explored for applications including thermoelectrics, lithium-ion battery electrodes, and catalysis.

Purpose of the Study:

  • To synthesize W-Nb-O oxide bronzes using the hydrothermal method.
  • To investigate the effects of thermal treatments on the structural and surface properties of these bronzes.
  • To understand the relationship between material composition, structure, and catalytic performance in glycerol dehydration.

Main Methods:

  • Hydrothermal synthesis of W-Nb-O oxide bronzes with varying Nb/(W + Nb) ratios.
  • Bulk and surface characterization techniques, including X-ray Photoelectron Spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR).
  • Thermal treatments to study structural evolution and surface chemistry.

Main Results:

  • Thermal treatments led to loss of long-range order and removal of NH4+ and H2O species.
  • W-Nb-O bronzes with ~50% Nb retained long-range order, attributed to a Cs0.5[W2.5Nb2.5O14]-type structure.
  • Increased Nb content stabilized surface W5+ species and increased surface Lewis acid sites, linked to NbO7 pentagonal bipyramid structures.

Conclusions:

  • Pseudocrystalline W-Nb-O oxides with Nb at% ≥ 50% exhibit enhanced Lewis acidity.
  • The stabilization of Lewis acid sites promotes the formation of heavier compounds during glycerol dehydration, reducing acrolein production.