The goal of this study is to provide insight into the mechanism of the oxygen reduction reaction on the TiO₂ rutile (1 1 0) surface in the presence of bridging hydroxyl groups. Considering the Langmuir–Hinshelwood and Eley–Rideal mechanisms, each possible intermediate was identified using density functional theory and a cluster model along with the energy barriers of the reduction steps and the OO bond breaking. Our results show that the initial step, the O₂ adsorption on the surface, is favored compared to the pure surface. At higher potentials, the oxygen reduction reaction was found to go through the formation of HO₂, which can easily convert to two terminal hydroxyl groups. The rate-limiting step is the desorption of the first H₂O with 0.58 eV energy requirement at zero applied potential, while at 1.23 V the reduction of the adsorbed OH to form H₂O is the bottleneck with a barrier height of 1.71 eV.

这项研究的目的是在存在桥连羟基的情况下，洞悉TiO ₂金红石（1 1 0）表面上的氧还原反应的机理。考虑到Langmuir-Hinshelwood和Eley-Rideal机理，使用密度泛函理论和聚类模型以及还原步骤和O O键断裂的能垒，确定了每种可能的中间体。我们的结果表明，与纯表面相比，初始步骤（表面上的O ₂吸附）更为有利。在较高的电势下，发现氧还原反应经历了HO ₂的形成，该HO ₂可以轻松转化为两个末端羟基。限速步骤是第一H ₂的解吸在零施加电势下具有0.58 eV能量需求的O，而在1.23 V时，被吸附的OH还原形成H ₂ O的障碍是势垒高度为1.71 eV的瓶颈。