Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

A frontier challenge in single‐atom (SA) catalysis is the design of fully inorganic sites capable of emulating the high reaction selectivity traditionally exclusive of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in SA sites, via the exploitation of the oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen‐defective SnO(2) uniquely unite excellent TOF with essentially full selectivity in the gas‐phase hydroformylation of ethylene, inhibiting the thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and surface characterization suggest that substantial depletion of the catalyst surface in lattice oxygen, energetically facile on SnO(2), is key to unlock a high coordination pliability at the mononuclear Rh centers, leading to an exceptional performance which is on par with that of molecular catalysts in liquid media.