Direct in-situ insights into the asymmetric surface reconstruction of rutile TiO2 (110)

The reconstruction of rutile TiO 2 (110) holds significant importance as it profoundly influences the surface chemistry and catalytic properties of this widely used material in various applications, from photocatalysis to solar energy conversion. Here, we directly observe the asymmetric surface reconstruction of rutile TiO 2 (110)-(1×2) with atomic-resolution using in situ spherical aberration-corrected scanning transmission electron microscopy. Density functional theory calculations were employed to complement the experimental observations. Our findings highlight the pivotal role played by repulsive electrostatic interaction among the small polarons −formed by excess electrons following the removal of neutral oxygen atoms− and the subsequent surface relaxations induced by these polarons. The emergence and disappearance of these asymmetric structures can be controlled by adjusting the oxygen partial pressure. This research provides a deeper understanding, prediction, and manipulation of the surface reconstructions of rutile TiO 2 (110), holding implications for a diverse range of applications and technological advancements involving rutile-based materials. The reconstruction of rutile TiO2 (110) impacts its surface chemistry and catalytic properties. Here, the authors offer a detailed understanding of the asymmetric surface reconstruction of TiO2 (110)-(1×2) through a combination of STEM and DFT calculations.