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 Pdn 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%).

Highly-Ordered PdIn Intermetallic Nanostructures Obtained from Heterobimetallic Acetate Complex: Formation and Catalytic Properties in Diphenylacetylene Hydrogenation.

Formation of PdIn intermetallic nanoparticles supported on α-Al2O3 was investigated by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and hydrogen temperature-programmed desorption (H2-TPD) methods. The metals were loaded as heterobimetallic Pd(µ-O2CMe)4In(O2CMe) complex to ensure intimate contact between Pd and In. Reduction in H2 at 200 °C resulted in Pd-rich PdIn alloy as evidenced by XRD and the disappearance of Pd hydride. A minor amount of Pd1In1 intermetallic phase appeared after reduction at 200 °C and its formation was accomplished at 400 °C. Neither monometallic Pd or in nor other intermetallic structures were found after reduction at 400⁻600 °C. Catalytic performance of Pd1In1/α-Al2O3 was studied in the selective liquid-phase diphenylacetylene (DPA) hydrogenation. It was found that the reaction rate of undesired alkene hydrogenation is strongly reduced on Pd1In1 nanoparticles enabling effective kinetic control of the hydrogenation, and the catalyst demonstrated excellent selectivity to alkene.

Selective Single-Site Pd-In Hydrogenation Catalyst for Production of Enhanced Magnetic Resonance Signals using Parahydrogen.

Pd-In/Al2 O3 single-site catalyst was able to show high selectivity (up to 98 %) in the gas phase semihydrogenation of propyne. Formation of intermetallic Pd-In compound was studied by XPS during reduction of the catalyst. FTIR-CO spectroscopy confirmed single-site nature of the intermetallic Pd-In phase reduced at high temperature. Utilization of Pd-In/Al2 O3 in semihydrogenation of propyne with parahydrogen allowed to produce ≈3400-fold NMR signal enhancement for reaction product propene (polarization=9.3 %), demonstrating the large contribution of pairwise hydrogen addition route. Significant signal enhancement as well as the high catalytic activity of the Pd-In catalyst allowed to acquire 1 H MR images of flowing hyperpolarized propene gas selectively for protons in CH, CH2 and CH3 groups. This observation is unique and can be easily transferred to the development of a useful MRI technique for an in situ investigation of selective semihydrogenation in catalytic reactors.