To reduce the emissions of internal combustion engines, ceria-based catalysts have been widely investigated as possible alternatives to the more expensive noble metals. In the present work, a set of four different ceria-based materials was prepared via hydrothermal synthesis, studying the effect of Cu and Mn as dopants both in binary and ternary oxides. In situ Raman analyses were carried out to monitor the behaviour of defect sites throughout thermal cycles and during the soot oxidation reaction. Despite ceria doped with 5% of Cu featured the highest specific surface area, reducibility and amount of intrinsic and extrinsic defects, a poor soot oxidation activity was observed through the standard activity tests. This result was confirmed by the calculation of soot conversion curves obtained through a newly proposed procedure, starting from the Raman spectra collected during the in situ tests. Moreover, Raman analyses highlighted that new defectiveness was produced on the Cu-doped catalyst at high temperature, especially after soot conversion, while a slight increase of the defect band and a total reversibility were observed in case of the ternary oxide and pure/Mn-doped ceria, respectively. The major increment was related to the extrinsic defects component; tests carried out in different atmospheres suggested the assignment of this feature to vacancy-free sites containing oxidized doping cations. Its increase at the end of the tests can be an evidence of peroxides and superoxides deactivation on catalysts presenting excessive oxygen vacancy concentrations. Instead, ceria doped with 5% of Mn exhibited the best soot oxidation activity, thanks to an intermediate density of oxygen vacancies and to its well-defined morphology.

Surface-enhanced Raman scattering (SERS) is a powerful and sensitive technique for the detection of fingerprint sig-nals of molecules and for the investigation of a series of surface chemical reactions. Many studies introduced quantita-tive applications of SERS in various fields and several SERS methods have been implemented for each specific applica-tion, ranging in performance characteristics, analytes used, instruments, and analytical matrices. In general, very few methods have been validated according to international guidelines. As a consequence, the application of SERS in high-ly-regulated environments is still considered risky and the perception of a poorly reproducible and insufficiently robust analytical technique has persistently retarded its routine implementation. Collaborative trials are a type of interlabora-tory study (ILS) frequently performed to ascertain the quality of a single analytical method. The idea of an ILS of quan-tification with SERS arose within the framework of Working Group 1 (WG1) of the COST Action BM1401 Ra-man4Clinics32 in an effort to overcome the problematic perception of quantitative SERS methods. Here we report the first interlaboratory SERS study ever conducted, involving 15 laboratories and 41 researchers. In this study we tried to define a methodology to assess the reproducibility and trueness of a quantitative SERS method, and to compare differ-ent methods. In our opinion, this is a first important step toward a “standardization” process of SERS protocols, not proposed by a single laboratory but by a larger community.