Encapsulated Heterogeneous Rhodium Single‐Atom Catalysts for Linear Selective Hydroformylation of 1‐Octene

Heterogeneous single-atom catalysts (SACs) remain underexplored for linear selective hydroformylation of higher olefins. Herein, practical-to-synthesize, highly stable, highly active and linear selective encapsulated heterogeneous rhodium SACs (0.07 wt% Rh₁@MFI-K) are reported for in situ activation and hydroformylation of 1-octene (>99% conversions, l/b >99, >1073 TONs and TOF >89 h^-1). Importantly, the optimized SAC 0.07 wt% Rh₁@MFI-K-0.8 demonstrates fourfolds turnover numbers and 28.5 times linear selectivity of that of the subnano-catalyst 0.15 wt% Rh@MFI-K-0. Spectroscopy characterizations confirm the atomically encapsulation of Rh within MFI zeolite channels.