Pocketlike Active Site of Rh1/MoS2 Single-Atom Catalyst for Selective Crotonaldehyde Hydrogenation

Selective hydrogenation of unsaturated aldehydes to unsaturated alcohols is a valuable but challenging task for synthesizing fine chemicals. We report that single Rh atoms anchored to the edges of 2D MoS₂ sheets can efficiently convert crotonaldehyde to crotyl alcohol with 100% selectivity via a steric confinement effect of pocketlike active sites. Characterization results suggest that the synthesized Rh₁/MoS₂ single-atom catalysts (SACs) possess a unique geometric and electronic configuration, which confines the adsorption mode of the reactant molecule by a steric effect. The DFT calculations suggest that the MoS₂ sheets terminate with oxidized Mo edges and the Rh₁ stably anchors at the Mo cation vacancy site, which can facilely dissociate H₂ to H atoms. The dissociated H atoms spill over to react with the edge O atoms to form OH species and create an HO-Mo-Rh₁-Mo-OH configuration, resembling a pocketlike active site, which confines the adsorption mode of the crotonaldehyde due to steric effects. Such specific adsorption configuration yields 100% selectivity. The strategy of constructing pocketlike active centers with single metal atoms and 2D nanosheets opens new approaches to designing highly selective SACs for specific classes of catalytic transformations.