Heteroatom‐Containing Zeolites as Solid Lewis Acid Catalysts for the Cycloaddition of CO₂ to Epoxides

Abstract The catalytic cycloaddition of CO 2 to epoxides to produce valuable cyclic carbonates represents a simple and promising strategy for CO 2 utilization, circumventing the ineffective CO 2 reduction process. Despite current progresses, there remains an impending demand for highly‐active, cost‐effective and stable catalysts especially the ideal heterogeneous catalytic systems. Herein, we report the preparation of heteroatom‐containing zeolites through a two‐step process comprising of framework dealumination and subsequent heteroatom incorporation, and their catalytic applications in CO 2 cycloaddition to epoxides. Characterization results reveal the successful incorporation of heteroatoms into framework to derive Lewis acidic M‐Beta zeolites (M = Ti, Zr or Hf). The as‐prepared M‐Beta Lewis acids show remarkable performance in the model reaction of CO 2 cycloaddition to propylene oxide with the assistance of potassium iodide under solvent‐free conditions. The reaction parameters have been optimized employing Ti‐Beta catalyst and the substrate scope has been investigated. Finally, the impact of Lewis acidity on the cycloaddition reaction is discussed and the actual bifunctional Ti‐Beta/KI catalyst system is proposed, which is of important significance for the understanding of CO 2 catalytic cycloaddition to epoxides.