Zeolite-Encaged Single-Atom Rhodium Catalysts: Highly-Efficient Hydrogen Generation and Shape-Selective Tandem Hydrogenation of Nitroarenes

Single-atom catalysts are emerging as a new frontier in heterogeneous catalysis because of their maximum atom utilization efficiency, but they usually suffer from inferior stability. Herein, we synthesized single-atom Rh catalysts embedded in MFI-type zeolites under hydrothermal conditions and subsequent ligand-protected direct H₂ reduction. C_s-corrected scanning transmission electron microscopy and extended X-ray absorption analyses revealed that single Rh atoms were encapsulated within 5-membered rings and stabilized by zeolite framework oxygen atoms. The resultant catalysts exhibited excellent H₂ generation rates from ammonia borane (AB) hydrolysis, up to 699 min⁻¹ at 298 K, representing the top level among heterogeneous catalysts for AB hydrolysis. The catalysts also showed superior catalytic performance in shape-selective tandem hydrogenation of various nitroarenes by coupling with AB hydrolysis, giving >99 % yield of corresponding amine products.