The atoms at the surface that constitute reactive sites clearly govern surface chemistry. But subsurface atoms, particularly substitutional and/or interstitial defects, can also influence surface chemistry, though a detailed understanding is still emerging. Here we report the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO₂, a prototypical metal oxide. Importantly, it contains both surface and subsurface intrinsic point-defects in the reduced state (along with residual extrinsic defects). Our scanning tunneling microscopy results show that O vacancies (V_O’s), the dominant surface defects, are virtually absent in the vicinity of positively-charged subsurface point-defects. Such anticorrelation of defects is consistent with density functional theory (DFT) calculations of the impact of subsurface defect proximity on V_O formation energy, which narrows down the possible candidates to certain interstitial defects, of both intrinsic and extrinsic nature. To monitor the influence of such (electron-donor type) defects on surface redox chemistry, a test reaction of the electron-mediated dissociative adsorption of O₂ is employed, which is observed to be suppressed around these defects. DFT results attribute this to a perceived absence of the intrinsic (Ti) (and likely extrinsic) interstitials in the nearest subsurface layer beneath “inhibited” areas, while the underlying energetic driver is largely repulsive electrostatics. Finally, we postulate that the entire subsurface region up to several atomic layers deep could be voided of any charged point-defects, whereas such defects are proposed to exist beyond the subsurface region. Subsequently, prevalent V_O’s are largely responsible for both the surface/subsurface reduction and mediation of the redox chemistry at reduced TiO₂(110) surface. Overall, this work provides new fundamental insights into the relation between surface and subsurface defects. In a broader perspective, the uncovered effects may prove to be general for other reducible oxides, and thus have potential implications in such diverse research fields as environmental remediation or microelectronics.

Considerable interest in understanding interfacial phenomena occurring across nanostructured solid oxide fuel cell (SOFC) membrane electrode assemblies has increased demand for in situ characterization techniques with higher resolution. We briefly outline recent advancements in atomic force microscopy (AFM) instrumentation and sub-systems in realizing real time imaging at high temperatures and ambient pressures, and the use of these in situ, multi-stimuli probes in collecting local information related to physical and fundamental processes. Here we demonstrate direct probing of local surface potential gradients related to the ionic conductivity of yttria-stabilized zirconia (YSZ) within symmetric SOFCs under intermediate operating temperatures (500 °C – 600 °C) via variable temperature scanning surface potential microscopy (VT-SSPM). The conductivity values obtained at different temperatures are then used to estimate the activation energy. These locally collected conductivity and activation energy values are subsequently compared to macroscopic electrochemical impedance results and bulk literature values, thus supporting the validity of the approach.