La0.7(Ca, Sr)0.3Ni0.6Mn0.5O3 perovskites for photothermal catalytic reforming of toluene: The role of oxygen species in the photothermal synergistic effect

Photothermal steam reforming (PTR) has emerged as an attractive approach for catalytic tar removal, due to the excitation of the photothermal synergistic effect. However, the role of oxygen species in PTR is still unclear. In this paper, the effect of alkaline earth metals (Ca and Sr) A-site-substitution on perovskite LaNi0.6Mn0.5O3 was investigated to reveal the role of oxygen species in PTR. The substitution of alkaline earth metals into perovskite lattice affected the dispersion of nickel and significantly adjusted the active oxygen species content on the catalyst surface. Oxygen species are crucial to the carbon deposition behavior of catalysts in PTR. La0.7Ca0.3Ni0.6Mn0.5O3 was rich in reactive oxygen species, which effectively inhibited the deposition and graphitization of coke, resulting in its good coke resistance and catalytic stability in PTR. Ultraviolet–visible light (UV–vis) supported the formation of oxygen vacancies and the dissociation of H2O to hydroxyl radicals through the photochemical reaction, which ultimately increased the surface adsorbed oxygen contents. Meanwhile, UV–vis promoted the migration and reaction of lattice oxygen. The photoactivation of oxygen species by UV–vis effectively enriched active oxygen species and improved the coke resistance, which resulted in enhanced catalytic stability of PTR at low-temperature.