The Metal-Oxide Nanoparticle–Aqueous Solution Interface Studied by Liquid-Microjet Photoemission

[Image: see text] The liquid-microjet technique combined with soft X-ray photoelectron spectroscopy (PES) has become an exceptionally powerful experimental tool to investigate the electronic structure of liquid water and nonaqueous solvents and solutes, including nanoparticle (NP) suspensions, since its first implementation at the BESSY II synchrotron radiation facility 20 years ago. This Account focuses on NPs dispersed in water, offering a unique opportunity to access the solid–electrolyte interface for identifying interfacial species by their characteristic photoelectron spectral fingerprints. Generally, the applicability of PES to a solid–water interface is hampered due to the small mean free path of the photoelectrons in solution. Several approaches have been developed for the electrode–water system and will be reviewed briefly. The situation is different for the NP–water system. Our experiments imply that the transition-metal oxide (TMO) NPs used in our studies reside close enough to the solution–vacuum interface that electrons emitted from the NP–solution interface (and from the NP interior) can be detected. We were specifically exploring aqueous-phase TMO NPs that have a high potential for (photo)electrocatalytic applications, e.g., for solar fuel generation. The central question we address here is how H(2)O molecules interact with the respective TMO NP surface. Liquid-microjet PES experiments, performed from hematite (α-Fe(2)O(3), iron(III) oxide) and anatase (TiO(2), titanium(IV) oxide) NPs dispersed in aqueous solutions, exhibit sufficient sensitity to distinguish between free bulk-solution water molecules and those adsorbed at the NP surface. Moreover, hydroxyl species resulting from dissociative water adsorption can be identified in the photoemission spectra. An important aspect is that in the NP(aq) system the TMO surface is in contact with a true extended bulk electrolyte solution rather than with a few monolayers of water, as is the case in experiments using single-crystal samples. This has a decisive effect on the interfacial processes that can occur since NP–water interactions can be uniquely investigated as a function of pH and provides an environment allowing for unhindered proton migration. Our studies confirm that water is dissociatively adsorbed at the hematite surface and molecularly adsorbed at the TiO(2) NP surface at low pH. In contrast, at near-basic pH the water interaction is dissociative at the TiO(2) NP surface. The liquid-microjet measurements presented here also highlight the multiple aspects of photoemission necessary for a full characterization of TMO nanoparticle surfaces in aqueous environments. For instance, we exploit the ability to increase species-specific electron signals via resonant photoemission, so-called partial electron yield X-ray absorption (PEY-XA) spectra, and from valence photoelectron and resonant Auger-electron spectra. We also address the potential of these resonance processes and the associated ultrafast electronic relaxations for determining charge transfer or electron delocalization times, e.g., from Fe(3+) located at the hematite nanoparticle interface into the aqueous-solution environment.