ABSTRACT
We investigated the possibility of synthesizing Co nanoparticles in CoZrnH/AlOx(OH)y/Al ceramic-metal catalysts and controlling the catalytic properties of these nanoparticles in syngas conversion by changing the Co/Zr ratio. The CoZr nanocomposites were obtained from metal powders by mechanochemical activation in a high-energy mill under an argon atmosphere, followed by treatment with hydrogen at high pressure and room temperature. Ceramic-metal catalysts were prepared by mixing the corresponding CoZrnH powder nanocomposite (30 wt%) with powdered aluminum (70 wt%), hydrothermal treatment of the mixture and subsequent calcination. The materials were characterized with a set of physicochemical methods: powder X-ray diffraction, scanning electron microscopy, 59Co internal field nuclear magnetic resonance spectroscopy, and temperature programmed reduction. Catalytic studies were performed in a laboratory fixed-bed flow reactor at 2 MPA and 210-270 °C. It is shown that the activity in syngas conversion to C5+ hydrocarbons and selectivity to methane and C2-C4 hydrocarbons depend on the Co/Zr ratio. Thus, with an increase in the zirconium content in the samples, the interaction of metal cobalt with metal zirconium improves in the process of mechanical activation and subsequent treatment with hydrogen. The destruction of the agglomerates of crystallites of metallic cobalt in the form of ß-Co (Cofcc) occurs as well as their transformation to α-Co (Cohcp) particles active in the syngas conversion to C5+ hydrocarbons. This can explain the highest specific yield of C5+ hydrocarbons on a cermet with the lowest Co/Zr ratio.
ABSTRACT
A mixed oxide of silver and nickel AgNiO2 was obtained via co-precipitation in alkaline medium. This oxide demonstrates room temperature activity in the reaction of ethylene epoxidation with a high selectivity (up to 70%). Using the PDF method, it was found that the initial structure of AgNiO2 contains stacking faults and silver vacancies, which cause the nonstoichiometry of the oxide (Ag/Ni < 1). It has been established that on the initial surface of AgNiO2 oxide, silver state can be considered as an intermediate between Ag2O and Ag0 (i.e. Agδ+-like), while nickel is characterized by signs of a deeply oxidized state (Ni3+-like). The interaction of AgNiO2 with C2H4 at room temperature leads to the simultaneous removal of two oxygen species with Eb(O 1s) = 529.0 eV and 530.5 eV considered as nucleophilic and electrophilic oxygen states, respectively. Nucleophilic oxygen was attributed to the lattice oxygen (Ag-O-Ni), while the electrophilic species with epoxidation activity was associated with the weakly bound oxygen stabilized on the surface. According to the TPR-C2H4 data, a large number of weakly bound oxygen species were found on the pristine AgNiO2 surface. The removal of such species at room temperature didn't result in noticeable structural transformation of delafossite. As the temperature of ethylene oxidation over AgNiO2 increased, the appearance of Ag0 particles was first observed below 200 °C followed by the complete destruction of the delafossite structure at higher temperatures.
ABSTRACT
The local structure of the active sites is one of the key aspects of establishing the nature of the catalytic activity of the systems. In this work, a detailed structural investigation of the Rh-CeO2 catalysts prepared by the co-precipitation method was carried out. The application of a variety of physicochemical methods such as XRD, Raman spectroscopy, XPS, TEM, TPR-H2, and XAS revealed the presence of highly dispersed Rh3+ species in the catalysts: Rh3+ single ions and RhOx clusters. The substitution of Ce4+ ions by Rh3+ species, which provided a strong distortion of the CeO2 lattice, is shown. XAS data ensured the refinement of the Rh local structure. It was shown that single Rh3+ sites located next to each other can merge the formation of RhOx clusters with Rh local environment close to the one in Rh2O3 and CeRh2O5 oxides. The distortion of the CeO2 lattice around single and cluster rhodium species had a beneficial effect on the catalytic activity of the samples in low-temperature CO oxidation (LTO-CO). TEM, XAS, and in situ XRD data allowed establishing the structural transformations of the catalysts under Red-Ox treatments. The reduction treatment led to Rhn metallic cluster formation localized on defects of the reduced CeO2-δ. The reduced sample demonstrated efficient CO conversion at 0 °C. However, this system was not stable: its contact with air led to ceria reoxidation and partial reoxidation of Rh to highly dispersed Rh3+ species at room temperature, while heating in an oxidizing atmosphere resulted in the complete reoxidation of metallic rhodium species. The results of the work shed light on the structural aspects of the reversibility of the Rh-CeO2 catalysts based on the highly dispersed Rh3+ species under treatment in the reaction conditions.
ABSTRACT
Highly dispersed LaCo1-x-yCuxTiyO3/KIT-6 perovskites were synthesized by the citrate method with inert mesoporous KIT-6 addition. The KIT-6 matrix was removed by dissolution in 7% NaOH aqueous solution. The dispersity of perovskites probably varies depending on the largest cation and its content at the B position of the perovskite ABO3 structure. The CoS=23+/CoS=03+ ratio increases with the increase in copper content and in the presence of Ti4+. It may be explained by the compensation of the distortion of the perovskite structure. The maximum syngas conversion is achieved at nCo/nCu = 7/3. At a higher copper content, the activity of the samples decreases due to the formation of large copper particles (up to 40 nm) in the course of the reduction. The selectivity for alcohols increases with an increase in the proportion of copper and reaches maximum values at a ratio of nCo/nCu close to 1. The distribution of alcohols is the same for all samples, except for LaCo0.35Cu0.35Ti0.3O3/KIT-6. It can be assumed that the synthesis of alcohols proceeds on bimetallic CoCu particles 3 nm in size and cobalt particles 4-6 nm in size, most likely enriched with copper on the surface.
ABSTRACT
In this work, the reaction properties of mixed silver-nickel oxide AgNiO2 were investigated in the reaction of CO oxidation ranging from room temperature up to 350 °C. X-ray photoelectron spectroscopy revealed the presence of a single oxidized silver state and the combination of Ni2+ and Ni3+ species on the surface of the as-prepared mixed oxide. It was established that AgNiO2 was able to interact with CO at room temperature. It was accompanied by the simultaneous titration of the lattice (O2--like) and weakly charged (O--like) oxygen species. The interaction with CO below 100 °C resulted in the accumulation of carbonate-like species on the AgNiO2 surface. Above 150 °C, the surface structure of mixed oxide was found to be disrupted, resulting in the formation of individual particles of metallic silver and oxidized nickel.
