Tailoring oxygen vacancies by synergy of dual metal cations in LaCo0.8M0.2O3 (M = Cu, Ni, Fe, Mn) towards catalytic oxidation of toluene

Abstract

Enhancing the catalytic performance of transition metal oxide catalysts is prerequisite for the efficient catalytic oxidation of VOCs. Here the B-site partially substituted LaCoO3 (LaCo0.8M0.2O3, M = Cu, Ni, Fe and Mn) catalysts was synthesized for the catalytic oxidation of toluene. Among these catalysts, LaCo0.8Ni0.2O3 catalyst exhibits remarkable catalytic performance for toluene with T50 = 226 °C and T90 = 239 °C at an initial toluene concentration of 1000 ppm, whose T50 (and T90) reduced by 13 °C (and 34 °C) compared with that of LaCoO3. Confirmed by BET, XPS, and EPR characterizations, Ni substitution improves the specific surface area, Co3+/Co2+ ratio, Oads/Olatt ratio, and oxygen vacancies concentration. This improvement indicates the improvement of adsorption and activation of reactant, mobility of oxygen species, thereby contributing to the superior catalytic performance in toluene oxidation. The B-site of LaCoO3 occupied by dual cations caused the lattice distortion and formation of oxygen vacancies due to the ionic radii difference between Co and Ni cations. Moreover, the apparent activation energy of LaCo0.8Ni0.2O3, as the determining factor for the catalytic oxidation rate, was remarkably reduced. Our findings confirmed the synergy effect of Co and Ni cations at B-site on the enhancement of catalytic activity, which provides a promising strategy for oxygen vacancy engineering.