Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 49, Pages 19289-19295Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b06628
Keywords
-
Categories
Funding
- National Science Foundation (USA) [CHE-1465057]
- National Natural Science Foundation of China [21908079, 51902339]
- Jiangnan University [1045210322190170]
- Ministry of Knowledge Economy, Korean government [20168510011350]
Ask authors/readers for more resources
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 Rh-1/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 Rh-1 stably anchors at the Mo cation vacancy site, which can facilely dissociate H-2 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-Rh-1-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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available