In₂O₃ Nanocrystals for CO₂ Fixation: Atomic-Level Insight into the Role of Grain Boundaries

N-functionalization of amines with CO₂ and H₂ is one of the most important processes to make use of CO₂. Although noble metal-based catalysts with remarkable performance have been widely used in this process, developing efficient non-noble-metal-based catalysts remains a grand challenge. Herein, we report In₂O₃ nanocrystals with high density of grain boundaries (HGB-In₂O₃), which show excellent activity toward methylation of amines. Impressively, HGB-In₂O₃ achieved the optimal yield of 82.7% for N,N-dimethylaniline with a mass activity of 21.2 mmol·g^-1h^-1 in methylation of N-methylaniline, comparable to noble-metal-based catalysts. As a bonus, HGB-In₂O₃ held noticeable stability, remarkable selectivity, and comprehensive applicability. Further mechanistic studies revealed that the presence of high density of grain boundaries not only facilitated the adsorption and activation of CO₂ to generate CH₃OH as the intermediate but also enhanced the activation of N-H bond in amines, contributing to the attractive activity of HGB-In₂O₃ toward methylation of amines.