Oxygen exchange at oxide/liquid and oxide/gas interfaces is important in technology and environmental studies, as it is closely linked to both catalytic activity and material degradation. The atomic-scale details are mostly unknown, however, and are often ascribed to poorly defined defects in the crystal lattice. Here we show that even thermodynamically stable, well-ordered surfaces can be surprisingly reactive. Specifically, we show that all the 3-fold coordinated lattice oxygen atoms on a defect-free single-crystalline “r-cut” (1 1 ¯ 02) surface of hematite (α-Fe2O3) are exchanged with oxygen from surrounding water vapor within minutes at temperatures below 70 °C, while the atomic-scale surface structure is unperturbed by the process. A similar behavior is observed after liquid-water exposure, but the experimental data clearly show most of the exchange happens during desorption of the final monolayer, not during immersion. Density functional theory computations show that the exchange can happen during on-surface diffusion, where the cost of the lattice oxygen extraction is compensated by the stability of an HO-HOH-OH complex. Such insights into lattice oxygen stability are highly relevant for many research fields ranging from catalysis and hydrogen production to geochemistry and paleoclimatology.

Jakub Z., Meier M., Kraushofer F., Balajka J., Pavelec J., Schmid M., et al. (2021). Rapid oxygen exchange between hematite and water vapor. NATURE COMMUNICATIONS, 12(1), 1-8 [10.1038/s41467-021-26601-4].

Rapid oxygen exchange between hematite and water vapor

Franchini C.
Supervision
;
2021

Abstract

Oxygen exchange at oxide/liquid and oxide/gas interfaces is important in technology and environmental studies, as it is closely linked to both catalytic activity and material degradation. The atomic-scale details are mostly unknown, however, and are often ascribed to poorly defined defects in the crystal lattice. Here we show that even thermodynamically stable, well-ordered surfaces can be surprisingly reactive. Specifically, we show that all the 3-fold coordinated lattice oxygen atoms on a defect-free single-crystalline “r-cut” (1 1 ¯ 02) surface of hematite (α-Fe2O3) are exchanged with oxygen from surrounding water vapor within minutes at temperatures below 70 °C, while the atomic-scale surface structure is unperturbed by the process. A similar behavior is observed after liquid-water exposure, but the experimental data clearly show most of the exchange happens during desorption of the final monolayer, not during immersion. Density functional theory computations show that the exchange can happen during on-surface diffusion, where the cost of the lattice oxygen extraction is compensated by the stability of an HO-HOH-OH complex. Such insights into lattice oxygen stability are highly relevant for many research fields ranging from catalysis and hydrogen production to geochemistry and paleoclimatology.
2021
Jakub Z., Meier M., Kraushofer F., Balajka J., Pavelec J., Schmid M., et al. (2021). Rapid oxygen exchange between hematite and water vapor. NATURE COMMUNICATIONS, 12(1), 1-8 [10.1038/s41467-021-26601-4].
Jakub Z.; Meier M.; Kraushofer F.; Balajka J.; Pavelec J.; Schmid M.; Franchini C.; Diebold U.; Parkinson G.S.
File in questo prodotto:
File Dimensione Formato  
PUBLISHED.pdf

accesso aperto

Tipo: Versione (PDF) editoriale
Licenza: Licenza per Accesso Aperto. Creative Commons Attribuzione (CCBY)
Dimensione 3.41 MB
Formato Adobe PDF
3.41 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/854847
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 10
  • ???jsp.display-item.citation.isi??? 8
social impact