ABSTRACT
Mn-based perovskites obtained by two different industrial procedures [flame spray pyrolysis (FSP) and co-precipitation (COP)] have been extensively compared in terms of chemical, structural, and morphological properties with the aim of evaluating how the upscale of complex catalysts can affect the functionality. The transition between laboratory and production scale is, in fact, usually not straightforward. The catalytic activity was tested focusing on reactions of relevance in the abatement of pollutants. In particular, CO-assisted NO reduction (which could be also considered as a model reaction) and reactions with a synthetic automotive exhaust mixture, including 10% steam and oxygen, were carried out. The development of three-way catalysts is still a relevant question: noble metal-free, efficient catalysts are even more necessary in hybrid vehicles. For this purpose, the catalytic activity of the samples has been correlated with the characterization results and thus with the peculiar aspects of the production method. Relevant differences have been observed between COP and FSP catalysts, in terms of the specific surface area, surface composition, and presence of surface-active sites. Also, the different efficiencies of inserting dopants in the perovskite unit cell and thus in reducibility and ion mobility are relevant. Despite having the same composition and crystalline structure, the catalytic activity and the effect of pre-treatments are observed to depend on the production procedure.
ABSTRACT
La0.6Ca0.2Fe0.8Cu0.2O3, undoped (LF) and Ca, Cu-doped (LCFC), powders, obtained by different industrial procedures, are compared to evaluate reproducibility and scale-up in different industrial synthetic approaches: flame spray pyrolysis (FSP) and coprecipitation (COP). Also the effects of varying composition (doping) and FSP process variability are considered as comparative studies on morphological, crystallographic, redox and compositional properties, and functional activity. A model reaction (CO + NO) and reactions with an automotive exhaust mixture were carried out. Unexpected results on the effectiveness of doping for catalytic activity emerged. Samples with the same compositions proved to be significantly affected by the synthesis, with variability within the same process. The activity of LCFC COP is comparable to the FSP analogue, at stoichiometric conditions, notwithstanding differences highlighted by characterization. In an oxygen-deficient mixture, LCFC-COP yields higher NO reduction and CO oxidation activity than LCFC-FSP. The absence of Ca in the lattice was unexpectedly beneficial. The doping effectiveness must be carefully checked for large-scale production.
