Nanocrystalline Ce1-xSmxO2-δ (x=0.4) solid solutions: structural characterization versus CO oxidation

A nanocrystalline Ce-Sm-oxide solid solution, with an excellent redox property and remarkable oxygen storage/release capacity, has been synthesized by means of a simple and highly practicable coprecipitation method. To understand the thermal and textural stability, the synthesized catalyst was subjected to calcination at various temperatures (773-1073 K). Physicochemical characterization was achieved using XRD, HRTEM, BET surface area, Raman, ICP-OES, XPS, TG-TDA, UV-vis DRS, TPR, and FTIR techniques, and the catalytic performance was evaluated for the oxidation of CO. Coprecipitation of Ce4+ and Sm3+ ions through ultra-high dilute solutions provided the single phase Ce0.6Sm0.4O2-delta solid solution in the nanoscale range, as confirmed by XRD and TEM studies. Raman studies revealed two types of lattice defects, namely, oxygen vacancies and MO8 complex defects due to disparity in the oxidation state and ionic radius of Sm3+ and Ce4+, respectively. Calculations made from XPS atomic ratios (Ce/Sm) and Raman band intensity ratios (A(D1)/A(F2g)) indicated migration of Sm from the bulk to the surface at elevated temperatures that caused a negative effect on the oxygen vacancy concentration. The doping of Sm3+ into the ceria lattice effectively enhanced the reduction behaviour of ceria by shifting the surface and bulk reduction to lower temperatures. Remarkably, Sm-incorporation showed an optimistic influence on the oxygen storage ability and CO oxidation efficiency of ceria attributed to profound lattice defects and enhanced bulk oxygen mobility. The salient features of physicochemical characterization versus catalytic CO oxidation efficiency of Ce-Sm-oxide solid solutions have been elaborated in this article.