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

Single-Atom Alloy Pd₁Ag₁₀/CeO₂–ZrO₂ as a Promising Catalyst for Selective Alkyne Hydrogenation

The effect of support on the performance of Pd1Ag10/Al2O3 and Pd1Ag10/CeO2–ZrO2 catalysts in the selective hydrogenation of diphenylacetylene (DPA) was studied. Characterization of the catalyst by DRIFTS-CO and HRTEM revealed the formation of a PdAg single-atom alloy (SAA) structure on the surface of PdAg nanoparticles, with Pd1 sites isolated by Ag atoms. It was found that the use of CeO2–ZrO2 as a carrier makes it possible to increase the activity of the Pd1Ag10 catalyst by a factor of three without loss of selectivity compared to the reference Pd1Ag10/Al2O3. According to the HRTEM data, this catalytic behavior can be explained by an increase in the dispersion of Pd1Ag10/CeO2–ZrO2 compared to its Pd1Ag10/Al2O3 counterpart. As evidenced by DRIFTS-CO data, the high selectivity of the Pd1Ag10/CeO2–ZrO2 sample presumably stems from the stability of the structure of isolated Pd1 sites on the surface of SAA Pd1Ag10/CeO2–ZrO2

Removal of VOCs by Ozone: n-Alkane Oxidation under Mild Conditions

Volatile organic compounds (VOCs) have a negative effect on both humans and the environment; therefore, it is crucial to minimize their emission. The conventional solution is the catalytic oxidation of VOCs by air; however, in some cases this method requires relatively high temperatures. Thus, the oxidation of short-chain alkanes, which demonstrate the lowest reactivity among VOCs, starts at 250–350 °C. This research deals with the ozone catalytic oxidation (OZCO) of alkanes at temperatures as low as 25–200 °C using an alumina-supported manganese oxide catalyst. Our data demonstrate that oxidation can be significantly accelerated in the presence of a small amount of O3. In particular, it was found that n-C4H10 can be readily oxidized by an air/O3 mixture over the Mn/Al2O3 catalyst at temperatures as low as 25 °C. According to the characterization data (SEM-EDX, XRD, H2-TPR, and XPS) the superior catalytic performance of the Mn/Al2O3 catalyst in OZCO stems from a high concentration of Mn2O3 species and oxygen vacancies

An Investigation into the Bulk and Surface Phase Transformations of Bimetallic Pd-In/Al2O3 Catalyst during Reductive and Oxidative Treatments In Situ

A series of oxidative treatments of PdIn-supported intermetallic nanoparticles at different temperatures were performed. The bulk and surface structure of catalyst during phase transformation was investigated by bulk- and surface-sensitive techniques (in situ XAFS, DRIFTS of adsorbed CO). It was found that comparison of palladium and indium fractions in bulk and on the surface suggests the formation of a «core-shell» structure. According to obtained results, the core consists of In-depleted intermetallic compound or inhomogeneous bimetallic phase with the inner core of metallic Pd, when a mixture of indium oxide, metallic palladium and small part of PdIn is present on the surface

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%)

Reversible Transformations of Palladium–Indium Intermetallic Nanoparticles upon Repetitive Redox Treatments in H₂/O₂

The transformations of chemical states and structures occurring in the PdIn/Al2O3 catalyst upon redox treatments in different gaseous atmospheres at different temperatures are addressed by an assortment of in situ bulk- (XRD) and surface-sensitive (XPS and DRIFTS CO) techniques. Any desired state of the catalyst between two opposite extremes of highly dispersed oxide species and regularly ordered PdIn intermetallic compound could be set in fully controlled and reversible ways by selecting appropriate conditions for the reductive treatment starting from the fully oxidized state. Since mutual conversions of multi-atomic Pdn centers into single-site Pd1 centers are involved in these transformations, the methodology could be used to find an optimum balance between the activity and selectivity of the catalytic system