Zn Single-Atom Catalysts Enable the Catalytic Transfer Hydrogenation of α<i>,</i>β-Unsaturated Aldehydes.

Chen, Jiawen; Xia, Yongming; Ling, Yuxuan; Liu, Xuehui; Li, Shuyuan; Yin, Xiong; Zhang, Lipeng; Liang, Minghui et al. · Nano Lett · 2024

basic_science · Level V

Where this comes from

Abstract

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N<sub>3</sub> moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, <i>in situ</i> FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N<sub>3</sub> moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.