Molecular species forming at the α-Fe2O3 nanoparticle–aqueous solution interface. Issue 19 (30th April 2018)

• Record Type: Journal Article
• Authors: Ali, Hebatallah; Seidel, Robert; Pohl, Marvin N.; Winter, Bernd
• Is Part Of: Chemical science. Volume 9:Issue 19(2018)
• Page Start: 4511
• Page End: 4523
• Publication Date: 2018-04-30
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c7sc05156e
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Local electronic-structure interaction, dissociative water adsorption, and electron-delocalization time at the α-Fe2 O3 nanoparticle–aqueous solution interface are revealed from liquid-jet photoelectron spectroscopy at the oxygen-1s and iron-2p resonances. Abstract : We report on electronic structure measurements of the interface between hematite nanoparticles (6 nm diameter) and aqueous solutions. Using soft X-ray photoelectron spectroscopy from a liquid microjet we detect valence and core-level photoelectrons as well as Auger electrons from liquid water, from the nanoparticle–water interface, and from the interior of the aqueous-phase nanoparticles. Most noteworthy, the method is shown to be sufficiently sensitive for the detection of adsorbed hydroxyl species, resulting from H2 O dissociation at the nanoparticle surface in aqueous solution. We obtain signal from surface OH from resonant, non-resonant, and from so-called partial-electron-yield X-ray absorption (PEY-XA) spectra. In addition, we report resonant photoelectron measurements at the iron 2p excitation. The respective Fe iron 2p3/2 edge (L3 -edge) PEY-XA spectra exhibit two main absorption peaks with their energies being sensitive to the chemical environment of the Fe 3+ ions at the nanoparticle–solution interface. This manifests in the 10 D q value which is a measure of the ligand-field strength. Furthermore, an observed intensity variation of the pre-peak, when comparing the PEY-XA spectra for different iron Auger-decay channels, can be assigned to different extents of electron delocalization. From the experimental fraction of local versus non-local autoionization signals we then find a very fast, approximately 1 fs, charge transfer time from interfacial Fe 3+ into the environment. The present study, which is complementary to ambient-pressure photoemission studies on solid-electrolyte systems, also highlights the multiple aspects of photoemission that need to be explored for a full characterization of the transition-metal-oxide nanoparticle surface in aqueous phase.