3 years ago

Metallic Cobalt to Spinel Co3O4Electronic Structure Evolution by Near-Ambient Pressure Photoelectron Spectroscopy

Metallic Cobalt to Spinel Co3O4Electronic Structure Evolution by Near-Ambient Pressure Photoelectron Spectroscopy
Ruchi Jain, Manoj Kumar Ghosalya, Kasala Prabhakar Reddy, Chinnakonda S. Gopinath
In the present study, valence band (VB) and core level photoelectron spectroscopy was carried out to investigate the electronic structural changes from polycrystalline Co to spinel Co3O4, via CoO at near ambient pressures (NAP; ∼0.1 mbar). O2–Co and H2–CoOx gas–solid oxidative and reductive interactions, respectively, have been explored with UV photons (He–I) or low kinetic energy electrons (≤16 eV) under NAP conditions. Typical VB features of Co metal, CoO, Co3O4, and a mixed phase between any two adjacent features were observed and well corroborated with core level changes. Very significant and characteristic changes were observed with Co 3d features in the VB for each stage from Co oxidation to Co3O4 as well as Co3O4 reduction to CoO. Co3O4 and CoO can be reversibly obtained by alternating the conditions between 0.1 mbar of H2 at 650 K and 0.1 mbar of O2 at 400 K, respectively. A meaningful correlation is observed between the changes in work function with cation oxidation state; small changes in the stoichiometry can strongly influence the shift in Fermi level and changes in work function under NAP conditions. Reversible work function changes are observed between oxidation and reduction conditions. While the O 2p derived feature for CoOx was observed at a constant BE (∼5 eV) throughout the redox conditions, the Co 3d band and molecular oxygen or hydrogen vibration feature shifts significantly underscoring the physicochemical changes, such as charge transfer energy and hence changes in satellite intensity. The peak close to EF originated from the 3d6L final state of the octahedral Co3+ 3d band of Co3O4.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b06661

DOI: 10.1021/acs.jpcc.7b06661

You might also like
Never Miss Important Research

Researcher is an app designed by academics, for academics. Create a personalised feed in two minutes.
Choose from over 15,000 academics journals covering ten research areas then let Researcher deliver you papers tailored to your interests each day.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.