Atomically Dispersed Palladium Catalyst for Chemoselective Hydrogenation of Quinolines.

Abstract

Chemoselective hydrogenation of quinoline and its derivatives is a significant strategy to achieve the corresponding 1,2,3,4-tetrahydroquinolines (py-THQ) for various potential applications. Here, we precisely constructed a titanium carbide supported atomically dispersed Pd catalyst (PdSA+NC/TiC) for quinoline hydrogenation, delivering above 99% py-THQ selectivity at complete conversion with an outstanding turnover frequency (TOF) of 463 h-1. AC-HAADF-STEM and XAFS demonstrate that the atomic dispersion of Pd includes Pd-Ti2C2 single atoms and Pd clusters with atomic-layer thickness. Theoretical calculation and experimental results revealed that H2 dissociation and subsequent hydrogenation rates were greatly promoted over Pd clusters. Although the adsorption of quinolines and intermediates are easier on Pd clusters than on Pd single atoms, the desorption of py-THQ is more favored over Pd single atoms than over Pd clusters. The desorption step may be the main reason for 5,6,7,8-tetrahydroquinoline (bz-THQ) and decahydroquinoline (DHQ) formation. Thus, a low reaction activity and py-THQ selectivity were received over PdSA/TiC and PdNP/TiC, respectively.