Molecular species forming at the α-Fe₂O₃ nanoparticle-aqueous solution interface

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 H₂O 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 2p_3/2 edge (L₃-edge) PEY-XA spectra exhibit two main absorption peaks with their energies being sensitive to the chemical environment of the Fe3+ ions at the nanoparticle–solution interface. This manifests in the 10D_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 Fe³⁺ 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