In order to increase their stability and tune-sensing characteristics, metal oxides are often surface-loaded with noble metals. Although a great deal of empirical work shows that surface-loading with noble metals drastically changes sensing characteristics, little information exists on the mechanism. Here, a systematic study of sensors based on rhodium-loaded WO₃, SnO₂, and In₂O₃—examined using X-ray diffraction, high-resolution scanning transmission electron microscopy, direct current (DC) resistance measurements, operando diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and operando X-ray absorption spectroscopy—is presented. Under normal sensing conditions, the rhodium clusters were oxidized. Significant evidence is provided that, in this case, the sensing is dominated by a Fermi-level pinning mechanism, i.e., the reaction with the target gas takes place on the noble-metal cluster, changing its oxidation state. As a result, the heterojunction between the oxidized rhodium clusters and the base metal oxide was altered and a change in the resistance was detected. Through measurements done in low-oxygen background, it was possible to induce a mechanism switch by reducing the clusters to their metallic state. At this point, there was a significant drop in the overall resistance, and the reaction between the target gas and the base material was again visible. For decades, noble metal loading was used to change the characteristics of metal-oxide-based sensors. The study presented here is an attempt to clarify the mechanism responsible for the change. Generalities are shown between the sensing mechanisms of different supporting materials loaded with rhodium, and sample-specific aspects that must be considered are identified.

Beginning with LaFeO₃, a prominent perovskite-structured material used in the field of gas sensing, various perovskite-structured materials were prepared using sol–gel technique. The composition was systematically modified by replacing La with Sm and Gd, or Fe with Cr, Mn, Co, and Ni. The materials synthesized are comparable in grain size and morphology. DC resistance measurements performed on gas sensors reveal Fe-based compounds solely demonstrated effective sensing performance of acetylene and ethylene. Operando diffuse reflectance infrared Fourier transform spectroscopy shows the sensing mechanism is dependent on semiconductor properties of such materials, and that surface reactivity plays a key role in the sensing response. The replacement of A-site with various lanthanoid elements conserves surface reactivity of AFeO₃, while changes at the B-site of LaBO₃ lead to alterations in sensor surface chemistry.

Near ambient pressure scanning photoelectron microscopy adds to the widely used photoemission spectroscopy and its chemically selective capability two key features: (1) the possibility to chemically analyse samples in a more realistic gas pressure condition and (2) the capability to investigate a system at the relevant spatial scale. To achieve these goals the approach developed at the ESCA Microscopy beamline at the Elettra Synchrotron facility combines the submicron lateral resolution of a Scanning Photoelectron Microscope with a custom designed Near Ambient Pressure Cell where a gas pressure up to 0.1 mbar can be achieved. In this manuscript a review of experiments performed with this unique setup will be presented to illustrate its potentiality in both fundamental and applicative research such as the oxidation reactivity and gas sensitivity of metal oxides and semiconductors. In particular, the capability to perform operando experiments with this setup opens the possibility to study operating devices and to properly address the real nature of the studied systems, because if microscopy and spectroscopy are simultaneously combined in a single technique it can yield to more conclusive results.