Nano TiO2 and Molybdenum/Tungsten Iodide Octahedral Clusters: Synergism in UV/Visible-Light Driven Degradation of Organic Pollutants

Emissions of various organic pollutants in the environment becomes a more and more acute problem in the modern world as they can lead to an ecological disaster in foreseeable future. The current situation forces scientists to develop numerous methods for the treatment of polluted water. Among these methods, advanced photocatalytic oxidation is a promising approach for removing organic pollutants from wastewater. In this work, one of the most common photocatalysts—titanium dioxide—was obtained by direct aqueous hydrolysis of titanium (IV) isopropoxide and impregnated with aqueous solutions of octahedral cluster complexes [{M6I8}(DMSO)6](NO3)4 (M = Mo, W) to overcome visible light absorption issues and increase overall photocatalytic activity. XRPD analysis showed that the titania is formed as anatase-brookite mixed-phase nanoparticles and cluster impregnation does not affect the morphology of the particles. Complex deposition resulted in the expansion of the absorption up to ~500 nm and in the appearance of an additional cluster-related band gap value of 1.8 eV. Both types of materials showed high activity in the photocatalytic decomposition of RhB under UV- and sunlight irradiation with effective rate constants 4–5 times higher than those of pure TiO2. The stability of the catalysts is preserved for up to 5 cycles of photodegradation. Scavengers’ experiments revealed high impact of all of the active species in photocatalytic process indicating the formation of an S-scheme heterojunction photocatalyst

Near-Ambient Pressure XPS and MS Study of CO Oxidation over Model Pd-Au/HOPG Catalysts: The Effect of the Metal Ratio

In this study, the dependence of the catalytic activity of highly oriented pyrolytic graphite (HOPG)-supported bimetallic Pd-Au catalysts towards the CO oxidation based on the Pd/Au atomic ratio was investigated. The activities of two model catalysts differing from each other in the initial Pd/Au atomic ratios appeared as distinctly different in terms of their ignition temperatures. More specifically, the PdAu-2 sample with a lower Pd/Au surface ratio (~0.75) was already active at temperatures less than 150 °C, while the PdAu-1 sample with a higher Pd/Au surface ratio (~1.0) became active only at temperatures above 200 °C. NAP XPS revealed that the exposure of the catalysts to a reaction mixture at RT induces the palladium surface segregation accompanied by an enrichment of the near-surface regions of the two-component Pd-Au alloy nanoparticles with Pd due to adsorption of CO on palladium atoms. The segregation extent depends on the initial Pd/Au surface ratio. The difference in activity between these two catalysts is determined by the presence or higher concentration of specific active Pd sites on the surface of bimetallic particles, i.e., by the ensemble effect. Upon cooling the sample down to room temperature, the reverse redistribution of the atomic composition within near-surface regions occurs, which switches the catalyst back into inactive state. This observation strongly suggests that the optimum active sites emerge under reaction conditions exclusively, involving both high temperature and a reactive atmosphere

Bimetallic Pd–Au/Highly Oriented Pyrolytic Graphite Catalysts: from Composition to Pairwise Parahydrogen Addition Selectivity

The model Pd and Au mono- and bi-metallic (Pd–Au) catalysts were prepared using vapor deposition of metals (Au and/or Pd) under ultrahigh vacuum conditions on the defective highly oriented pyrolytic graphite (HOPG) surface. The model catalysts were investigated using the X-ray photoelectron spectroscopy and scanning tunneling microscopy at each stage of the preparation procedure. For the preparation of bimetallic catalysts, different procedures were used to get different structures of PdAu particles (Au_shell–Pd_core or alloyed). All prepared catalysts showed rather narrow particles size distribution with an average particles size in the range of 4–7 nm. Parahydrogen-enhanced nuclear magnetic resonance spectroscopy was used as a tool for the investigation of Pd–Au/HOPG, Pd/HOPG, and Au/HOPG model catalysts in propyne hydrogenation. In contrast to Au sample, Pd, PdAu_alloy, and Au_shell–Pd_core samples were shown to have catalytic activity in propyne conversion, and pairwise hydrogen addition routes were observed. Moreover, bimetallic samples demonstrated the 2- to 5-fold higher activity in pairwise hydrogen addition in comparison to the monometallic Pd sample. It was shown that the structures of bimetallic Pd–Au particles supported on HOPG strongly affected their activities and/or selectivities in propyne hydrogenation reaction: the catalyst with the Au_shell–Pd_core structure demonstrated higher pairwise selectivity than that with the PdAu_alloy structure. Thus, the reported approach can be used as an effective tool for the synergistic effects investigations in hydrogenation reactions over model bimetallic Pd–Au catalysts, where the active component is supported on a planar support

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