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In this study, a set of CuCeOx catalysts was prepared via the coprecipitation method using a Multi-Inlet Vortex Reactor: the Cu wt.% content is 5, 10, 20, 30 and 60. Moreover, pure CeO2 and CuO were synthesized for comparison purposes. The physico-chemical properties of this set of samples were investigated by complementary techniques, e.g., XRD, N2 physisorption at −196 °C, Scanning Electron Microscopy, XPS, FT-IR, Raman spectroscopy and H2-TPR. Then, the CuCeOx catalysts were tested for the CO and ethene oxidation reactions. As a whole, all the prepared samples presented good catalytic performances towards the CO oxidation reaction (1000 ppm CO, 10 vol.% O2/N2): the most promising catalyst was the 20%CuCeOx (complete CO conversion at 125 °C), which exhibited a long-term thermal stability. Similarly, the oxidative activity of the catalysts were evaluated using a gaseous mixture containing 500 ppm C2H4, 10 vol.% O2/N2. Accordingly, for the ethene oxidation reaction, the 20%CuCeOx catalyst evidenced the best catalytic properties. The elevated catalytic activity towards CO and ethene oxidation was mainly ascribed to synergistic interactions between CeO2 and CuO phases, as well as to the high amount of surface-chemisorbed oxygen species and structural defects. [ABSTRACT FROM AUTHOR]

Copper-ceria mixed oxides are widely considered promising catalysts for oxidation reactions, especially when the participation of lattice oxygen is required. However, the mechanistic understanding of these catalytic systems is still incomplete, due to their considerable complexity. In fact, copper doping of ceria results in the formation of a significant number of different interacting sites in continuous evolution during the catalytic processes. In the present study, pure and Cu-doped ceria samples were deeply investigated through combined spectroscopic techniques, i.e. XPS, EPR, and in situ FTIR and Raman spectroscopy. Through this systematic approach, the copper sites and lattice defects responsible for the enhanced CO oxidation activity of doped ceria were elucidated. Superficial Cu+ species and small Cu0 clusters promote the adsorption of CO at low temperature, while isolated Cu2+ monomers and dimers well-dispersed in the ceria matrix foster lattice oxygen mobility, involving the sub-surface in the redox phenomena. Consequently, the structure of Cu-doped ceria undergoes substantial modifications throughout CO oxidation in the absence of O 2 , with the formation of oxygen vacancy clusters. Anyway, these changes are reversible, and structural reorganization in the presence of O 2 can occur even at room temperature. The excellent performance of Cu-doped ceria eventually stems from the effective cooperation among the different catalytic sites in the mixed oxide. [Display omitted] • The different defects and Cu sites in doped ceria are complementarily investigated. • Cu+ sites and small Cu0 clusters at the catalyst surface enhance CO adsorption. • Isolated Cu2+ monomers and dimers in the CeO 2 matrix foster lattice oxygen mobility. • Clusters of oxygen vacancies may form when the oxygen demand at the surface is high. • The effective cooperation of the different sites promotes ceria catalytic activity. [ABSTRACT FROM AUTHOR]

• CO oxidation was studied by in situ Raman spectroscopy on nanostructured ceria-based materials. • In situ Raman analyses during CO oxidation allowed to monitor defect sites in operando conditions. • Cycles of reduction (CO in N 2) and oxidation (pure O 2) at 400 °C allow to study the stability of defects. • Oxygen vacancies evolved from clusters to isolated ones according to the atmosphere and temperature. • The involvement of the defect sites in structural rearrangement is fostered by easily reducible dopants. Among the factors affecting ceria activity, the defectiveness plays a key role in the case of CO oxidation. In this study, its connection with the catalytic performance was investigated via in-situ Raman spectroscopy on nanostructured pure and Cu/Mn-doped ceria, monitoring the defect sites and surface species evolution during the reaction. The accumulation of polyene-like chains, formed through CO dissociative adsorption at the catalyst surface, was observed and their disappearance was related to the catalyst light-off temperature. Moreover, the doped samples exhibited a rise of the Raman bands associated to defects after the tests, consequence of the structural rearrangements occurring during CO oxidation. Indeed, in-situ Raman measurements during reduction (CO/N 2) and oxidation cycles at 400 °C evidenced the formation of oxygen vacancy clusters in reducing atmosphere, which could reorganize not only in O 2 but also upon a temperature decrease, forming isolated vacancies and then evolving in Frenkel and extrinsic oxidized dopant-containing sites when exposed to oxygen. [ABSTRACT FROM AUTHOR]

A Gasoline Particulate Filter (GPF) can be an effective solution to abate the particulate matter produced in modern direct injection gasoline engines. The regeneration of this system is critical, since it occurs in oxygen deficiency, but it can be promoted by placing an appropriate catalyst on the filter walls. In this paper, a nanostructured equimolar ceria-praseodymia catalyst, obtained via hydrothermal synthesis, was characterized with complementary techniques (XRD, N2-physisorption, FESEM, XPS, Temperature Programmed Reduction, etc.) and its catalytic performances were investigated in low oxygen availability. Pr-doping significantly affected ceria structure and morphology, and the weakening of the cerium–oxygen bond associated to Pr insertion resulted in a high reducibility. The catalytic activity was explored considering different reactions, namely CO oxidation, ethylene and propylene total oxidation, and soot combustion. Thanks to its capability of releasing active oxygen species, ceria-praseodymia exhibited a remarkable activity and CO2-selectivity at low oxygen concentrations, proving to be a promising catalyst for coated GPFs. [ABSTRACT FROM AUTHOR]