Yang Lou, Yongping Zheng, Xu Li
Nov 4, 2019
Citations
0
Influential Citations
110
Citations
Quality indicators
Journal
Journal of the American Chemical Society
Abstract
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 crotonalde-hyde to crotyl alcohol with 100% selectivity via a steric confinement effect of pocket-like 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 cati-on vacancy site, which can facilely dissociate H2 to H atoms. The dissociated H atoms spillover to react with the edge O atoms to form OH species and create an HO-Mo-Rh1-Mo-OH configuration, resembling a pocket-like 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 pocket-like active centers with single metal atoms and 2D nanosheets opens new approaches to designing high-ly selective SACs for specific classes of catalytic transformations.