摘要
Nanosized solid superacids SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2),as well as MCM-41-supported SO_(4)^(2−)/ZrO_(2),were prepared.Their structures,acidities,and catalytic activities were investigated and compared using XRD,N2 adsorption-desorption,and in situ FTIR-pyridine adsorption,as well as an evaluation reaction with pseudoionone cyclization.The results showed that SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)possess not only nanosized particles with diameters<7.0 nm,a BET sur-face greater than 140 cm2/g and relatively regular mesostruc-tures with pores around 4.0 nm,but also a pure anatase phase and strong acidity.Different from the Lewis acid nature of SO_(4)^(2−)/ZrO_(2)/MCM-41,SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)exhibit mainly Brønsted acidities.The strongest Brønsted acid sites were produced on SO_(4)^(2−)/TiO_(2)promoted with H2SO4,while Lewis acid sites on S_(2)O_(8)^(2)−/TiO_(2)even stronger than those on SO_(4)^(2−)/ZrO_(2)/MCM-41 were generated when persulfate solu-tion was used as sulfating agent.Because of their distinct acid natures,SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO_(4)^(2−)/ZrO_(2)/MCM-41.It can be concluded that the existence of more Brønsted acid sites was favorable for proton participation in the cyclization reaction.
