LAUSR

Selective activation of carbon‐oxygen bonds (like C−O and C=O) represents an essential part of the biomass conversion, but it is difficult to selectively activating the inert carbon‐oxygen bonds. We report 2D MoS2 edges confined single Pt atoms efficiently catalyze biomass‐derived crotonaldehyde to crotyl alcohol with selectivity from 90 to 100 %. The Pt1/MoS2 single‐atom catalysts have a unique HO−Mo−S−Pt1−S−Mo−OH configuration, reminiscent of an enzyme pocket‐like active site, which restricts the adsorption configuration of crotonaldehyde by a steric hindrance effect. The Pt1 atoms possess unique electronic structures due to the Pt1‐S4 configuration, which easily dissociates H2 to H species and boosts the activity. The activated H species spillover and react with O atoms on edges, forming OH and creating the HO−Mo−S−Pt1−S−Mo−OH configuration, which restricts the adsorption configuration of crotonaldehyde and yields high selectivity. The tactics of fabricating pocket‐like active sites with metal single atoms and 2D nanosheet edges shed a light on developing highly selective catalysts for biomass conversion reactions.