Liquid-phase hydrogenation of 1-phenyl-1-propyne on the Pd₁Ag₃/Al₂O₃ single-atom alloy catalyst: Kinetic modeling and the reaction mechanism

This research was focused on studying the performance of the Pd₁Ag₃/Al₂O₃ single-atom alloy (SAA) in the liquid-phase hydrogenation of di-substituted alkyne (1-phenyl-1-propyne), and development of a kinetic model adequately describing the reaction kinetic being also consistent with the reaction mechanism suggested for alkyne hydrogenation on SAA catalysts. Formation of the SAA structure on the surface of PdAg₃ nanoparticles was confirmed by DRIFTS-CO, revealing the presence of single-atom Pd₁ sites surrounded by Ag atoms (characteristic symmetrical band at 2046 cm⁻¹) and almost complete absence of multiatomic Pd_n surface sites (<0.2%). The catalyst demonstrated excellent selectivity in alkyne formation (95–97%), which is essentially independent of P(H₂) and alkyne concentration. It is remarkable that selectivity remains almost constant upon variation of 1-phenyl-1-propyne (1-Ph-1-Pr) conversion from 5 to 95–98%, which indicates that a direct alkyne to alkane hydrogenation is negligible over Pd₁Ag₃ catalyst. The kinetics of 1-phenyl-1-propyne hydrogenation on Pd₁Ag₃/Al₂O₃ was adequately described by the Langmuir-Hinshelwood type of model developed on the basis of the reaction mechanism, which suggests competitive H₂ and alkyne/alkene adsorption on single atom Pd₁ centers surrounded by inactive Ag atoms. The model is capable to describe kinetic characteristics of 1-phenyl-1-propyne hydrogenation on SAA Pd₁Ag₃/Al₂O₃ catalyst with the excellent explanation degree (98.9%).