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(3)-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(3)-based support exhibits unconventional size effect to Pd site, in which over-hydrogenation is greatly suppressed on Pd(1) 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(1)/MoWO(3) achieves recorded performance of 98.4% selectivity and 10200 h(-1) 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.