Mediating trade-off between activity and selectivity in alkynes semi-hydrogenation via a hydrophilic polar layer.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 38336938.
- Also identified by DOI 10.1038/s41467-024-45104-6 and PMC identifier 10858237.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
As a crucial industrial process for the production of bulk and fine chemicals, semi-hydrogenation of alkynes faces the trade-off between activity and selectivity due to undesirable over-hydrogenation. By breaking the energy linear scaling relationships, we report an efficient additive-free WO<sub>3</sub>-based single-atom Pd catalytic system with a vertical size effect of hydrogen spillover. Hydrogen spillover induced hydrophilic polar layer (HPL) with limited thickness on WO<sub>3</sub>-based support exhibits unconventional size effect to Pd site, in which over-hydrogenation is greatly suppressed on Pd<sub>1</sub> site due to the polar repulsive interaction between HPL and nonpolar C=C bonds, whereas this is invalid for Pd nanoparticles with higher altitudes. By further enhancing the HPL through Mo doping, activated Pd<sub>1</sub>/MoWO<sub>3</sub> achieves recorded performance of 98.4% selectivity and 10200 h<sup>-1</sup> activity for semi-hydrogenation of 2-methyl-3-butyn-2-ol, 26-fold increase in activity of Lindlar catalyst. This observed vertical size effect of hydrogen spillover offers broad potential in catalytic performance regulation.