Dynamic Evolution of Palladium Single Atoms on Anatase Titania Support Determines the Reverse Water–Gas Shift Activity

Research interest in single-atom catalysts (SACs) has been continuously increasing. However, the lack of understanding of the dynamic behaviors of SACs during applications hinders catalyst development and mechanistic understanding. Herein, we report on the evolution of active sites over Pd/TiO₂-anatase SAC (Pd₁/TiO₂) in the reverse water-gas shift (rWGS) reaction. Combining kinetics, in situ characterization, and theory, we show that at T ≥ 350 °C, the reduction of TiO₂ by H₂ alters the coordination environment of Pd, creating Pd sites with partially cleaved Pd-O interfacial bonds and a unique electronic structure that exhibit high intrinsic rWGS activity through the carboxyl pathway. The activation by H₂ is accompanied by the partial sintering of single Pd atoms (Pd₁) into disordered, flat, ∼1 nm diameter clusters (Pd_n). The highly active Pd sites in the new coordination environment under H₂ are eliminated by oxidation, which, when performed at a high temperature, also redisperses Pd_n and facilitates the reduction of TiO₂. In contrast, Pd₁ sinters into crystalline, ∼5 nm particles (Pd_NP) during CO treatment, deactivating Pd₁/TiO₂. During the rWGS reaction, the two Pd evolution pathways coexist. The activation by H₂ dominates, leading to the increasing rate with time-on-stream, and steady-state Pd active sites similar to the ones formed under H₂. This work demonstrates how the coordination environment and nuclearity of metal sites on a SAC evolve during catalysis and pretreatments and how their activity is modulated by these behaviors. These insights on SAC dynamics and the structure-function relationship are valuable to mechanistic understanding and catalyst design.