This study investigates the role of oxygen vacancy on Fe-doped CeO₂ catalyst activity for soot oxidation. The oxygen vacancy was assessed through Ce³⁺ content. The Fe content was varied between 0 and 30% for two catalyst preparation methods, co-precipitation (CP) and solution combustion synthesis (SCS). X-ray photoelectron spectroscopy indicates that ceria exists as both Ce₄₊ and Ce₃₊, while iron is present only as Fe₃₊. The catalyst’s activity was evaluated by ignition (T10) and combustion (T50) temperatures using thermogravimetric analysis. Optimum Fe contents yielding the highest activity were found to be 10% and 5% for CP and SCS catalysts, respectively. The surface area and morphology have shown moderate effect on catalyst activity, because catalytic soot oxidation involves solid-solid contact. More importantly, regardless of the fabrication method, it was found that Ce₃₊ content, which is closely related to oxygen vacancies, plays the most important role in affecting the catalyst activity.

This work focuses on the support effect on the performances of Co-based catalysts for the acetic acid steam reforming. SBA-15, a well ordered hexagonal mesoporous silica structure, and CeO2 have been selected as the supports, with the impact of chromium addition also being investigated. Better acetic acid steam reforming performances have been recorded for CeO2 compared to SBA-15 supported catalysts and, in particular, the 7Co/CeO2 catalyst showed the highest values of acetic acid conversions with enhanced H2 yields below 480°C, in comparison to the other investigated catalytic formulations. In addition, more pronounced coke depositions and acetone concentrations have been obtained with CeO2 supported catalysts, due to the tendency of ceria to catalyse the ketonization reaction. Chromium addition to Co/SBA-15 catalysts led to an enhancement in the activity towards acetic acid steam reforming, while on CeO2 supported catalysts no improvement in the catalysts activity was observed; however, on both SBA-15 and CeO2 supported catalysts, Cr addition reduced the amount of coke deposited on the catalysts surface.

Ceria, zirconia and mixed cerium-zirconium mesoporous oxides were synthesized and used as supports for sulfur and gold species. The materials were characterised using selected advanced techniques (ICP-OES, elemental analysis, XPS, XRD, N₂ adsorption and desorption isotherms, UV-vis, ATR-FTIR, TPR-H₂, TG-DTA) which allowed monitoring of the oxidation state of metals (cerium and gold) and the surface properties of the catalysts, in particular the concentration of the components on the surface and in the bulk of materials. The interactions between gold, sulfur and metals from oxides were considered. The goal of this work was studied the changes in the chemical composition of materials and the oxidation states of cerium species after the modification of oxides with sulfur and gold species and the estimation of the influence of these changes on the surface properties. The chemical composition of surface affects the mobility of surface oxygen and the oxidation state of cerium, which can play the role of redox sites (e.g. Ce³⁺/Ce⁴⁺ species), and therefore it strongly influences on the adsorption of hydrogen sulfide and then gold loading. Additionally, gold catalysts modified with sulfur species were tested in the reaction of glycerol oxidation in the liquid phase at basic conditions as the test reaction of the catalytic oxidation of organic pollutants from water.

The interaction between O2 and reduced ceria nanocubes was mainly investigated by FTIR spectroscopy. Nanorods and nanoparticles were also studied for comparison. Adsorption of O2 at 100 K on unreduced ceria produces only O2 molecularly adsorbed on Ce4+ sites. The Ce3+ cations in H2-reduced ceria were monitored by the 2F5/2 → 2F7/2 electronic transition band at 2133-2095 cm-1. This band possesses a fine structure well resolved at 100 K. The positions of the individual components depend on the Ce3+ environment, including the presence of nearby species such as OH groups. Even at 100 K, the interaction of O2 with reduced ceria leads to fast oxidation of about half of the Ce3+ cations, including all Ce3+ sites bound to OH groups and carbonates, and the simultaneous formation of superoxo (O2) and peroxo (O22) species. The remaining fraction of Ce3+ sites disappears upon heating up to 348 K. At higher temperatures, the peroxo species decompose directly, yielding lattice oxygen. Superoxides are converted to hydroperoxides, which then decompose to terminal OH groups. Reduced samples evacuated at T < 773 K contain sorbed H2. Part of this hydrogen is also fast oxidized to H2O even at 100 K.

Soot combustion experiments with 5%O2/He were conducted using model soot, and four distinct compositions of CexPr1-xO2-δ oxides were prepared, varying nominal cerium com-positions (x=0, 0.2, 0.3, and 1). The catalyst samples were comprehensively characterized using techniques such as XRD, Raman spectroscopy, HR-TEM, N2 adsorption at −196 °C, XPS, O2-TPD, H2-TPR, and work function measurements. The Pr-rich compositions, rang-ing from Ce0.3Pr0.7O2-δ to PrO2-δ, resulted in a significant increase in the total evolved O2 amounts and enhanced catalyst reducibility. However, a decrease in textural properties of the catalysts was noted, being particularly important for the pure praseodymia under the synthesis route conducted. The catalytic activity was investigated under two contact modes of mixing between soot and catalyst: loose and tight. The results revealed that the catalytic performance is associated with the surface contact in tight contact mode and with the combination of surface/subsurface/bulk oxygen mobility and the BET surface ar-ea in loose contact mode. Notably, the T10 and T50 parameters were achieved at much lower temperatures than the uncatalyzed soot combustion, even under loose contact conditions. Specifically, the 50% conversion was achieved at 511℃ and 538℃ for Ce0.3Pr0.7O2 and Ce0.2Pr0.8O2, respectively. While no direct correlation between catalytic activity and work function was observed a significant relationship emerges between work function values and the formation of oxy-gen vacancies, whatever the conditions used for these measurements. On the other hand, the ability to generate a high population of oxygen vacancies at low temperatures, rather than the direct activation of gas-phase O2, influences the catalytic performance of Pr-doped ceria catalysts, highlighting the importance of surface/subsurface oxygen vacancy generation, which was the parameter which showed better correlation with the catalytic activity, whatever the soot conversion value or the mode of contact considered.

This work is devoted to the study of active and stable nickel catalysts for methane dry reforming based on Pr-doped ceria-zirconia obtained by solvothermal continuous method. The studies of physicochemical and catalytic properties of the 5%Ni\Ce0.75Zr0.25-xPrxO2 series showed that Pr introduction leads to an increase in the amount of highly reactive oxygen of the oxide lattice. Praseodymium-based catalysts showed significantly higher reactant conversions. In addition to the nature of support, the method of nickel introduction was also studied - Ni was added both by impregnation and one-pot with mixed oxide preparation. The method of Ni addition was shown to have significant effect on the morphology of the supported active component and, respectively, on the catalytic activity. The 5%Ni/Ce0.75Zr0.15Pr0.1O2 catalyst prepared by one-pot method showed stable operation in the MDR reaction for 30 hours at CO2 and CH4 conversions of ~40% and an H2 yield of ~18% (Т=700°С, τ=10ms).

In this work, non-ordered and ordered CeO2-based catalysts are proposed for the CO2 conversion to dimethyl carbonate (DMC). Particularly, a non-ordered mesoporous CeO2, consisting of small nanoparticles of about 8 nm, is compared with two highly porous (635-722 m2/g) ordered CeO2@SBA-15 nanocomposites obtained by two different impregnation strategies (a two-solvent impregnation (TS) and a self-combustion (SC) method), with a final CeO2 loading of 10 wt%. The Rietveld analyses on XRD data combined with TEM imaging evidence the influence of the impregnation strategy on the dispersion of the active phase: nanoparticles of 8 nm for the TS composite vs. 3 nm for the SC composite. The catalytic results show comparable activity for the mesoporous ceria and the CeO2@SBA-15_SC nanocomposite, while a lower DMC yield was found for the CeO2@SBA-15_TS nanocomposite. This finding is presumably ascribed to a partial obstruction of the pores by the CeO2 nanoparticles in the case of the TS composite, which leads to a reduced accessibility of the active phase. On the other hand, in the case of the SC composite, where the CeO2 particle size is much lower than the pore size, there is an improved accessibility of the active phase to the molecules of the reactants.

Nitric acid is a key component in the production of nitrate fertilisers and is industrially produced using the Ostwald process. The Ostwald process can be further intensified by oxidising nitric oxide to nitrogen dioxide using heterogeneous catalysts. We have explored various monometallic and bimetallic catalysts for NO to NO2 oxidation and found ruthenium supported on ceria, containing 10 wt.% manganese to be a promising catalyst for oxidising NO to NO2 at low temperatures at industrially relevant conditions. For a feed comprising 10% NO, 6% O2, 15% H2O and rest Ar, and 8% NO, 2% NO2 5% O2, 15% H2O and rest Ar, the ruthenium-manganese catalysts attained NO-NO2 equilibrium below 400∘C. For the 5wt.% ruthenium and 10 wt.% manganese on ceria catalyst, an apparent activation energy of 39.4 kJ/mol and 85.4 kJ/mol were observed in the absence and presence of NO2, respectively. These findings demonstrate the potential of supported bimetallic ruthenium-manganese catalysts for efficient oxidation of NO to NO2 at low temperatures which can lead to significant process intensification of nitric acid plants.

A technique for fabrication of bacterial cellulose-based films with CeO₂ nanofiller has been developed. The structural and morphological characteristics of the materials have been studied, their thermal and mechanical properties in dry and swollen states having been determined. The preparation methodology makes it possible to obtain composites with a uniform distribution of nanoparticles. The catalytic effect of ceria regarding the thermal oxidative destruction of cellulose has been confirmed by TGA and DTA methods. An increase in CeO₂ content led to an increase in the elastic modulus (a 1.27-fold increase caused by the introduction of 5 wt.% of the nanofiller into the polymer) and strength of the films. This effect is explained by the formation of additional links between polymer macro-chains via the nanoparticles’ surface. The materials fabricated were characterised by a limited ability to swell in water. Swelling caused a 20- to 30-fold reduction in the stiffness of the material, the mechanical properties of the films in a swollen state remaining germane to their practical use. The application of the composite films in cell engineering as substrates for the stem cells’ proliferation has been studied. The increase in CeO₂ content in the films enhanced the proliferative activity of embryonic mouse stem cells. The cells cultured on the scaffold containing 5 wt.% of ceria demonstrated increased cell survival and migration activity. An analysis of gene expression confirmed improved cultivation conditions on CeO₂-containing scaffolds.