Acidic properties of sulfonic acid-functionalized FSM-16 mesoporous silica and its catalytic efficiency for acetalization of carbonyl compounds

• Published in: Journal of catalysis 2005-04, Vol.231 (1), p.131-138
• Main Authors: Shimizu, Ken-ichi, Hayashi, Eidai, Hatamachi, Tsuyoshi, Kodama, Tatsuya, Higuchi, Tomoya, Satsuma, Atsushi, Kitayama, Yoshie
• Format: Article
• Language: English
• Subjects: Acetalization; Catalysis; Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Mesoporous silica; Microcalorimetry; Porous materials; Sulfonic acid; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; TPD
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2005.01.017

Propyl-sulfonic acid-functionalized FSM-16 mesoporous silica (SO 3H-FSM) is prepared by a conventional post-modification method. For the acetalization of carbonyl compounds with ethylene glycol, SO 3H-FSM shows a higher rate and 1,3-dioxolane yield than conventional heterogeneous solid acids such as zeolites, montmorillonite K10 clay, silica-alumina, and the sulfonic resin. SO 3H-FSM is stable during the reaction, with no leaching and deactivation of sulfonic acid groups, and is reusable without loss of its activity. The acidity and hydrophilicity of SO 3H-FSM are well characterized by the microcalorimetry of NH 3 adsorption, NH 3-TPD, and H 2O-TPD, and the result is compared with those for various aluminosilicate zeolites (HZSM5, HBEA, HY) and K10 clay. It is found that NH 3-TPD is not suitable for characterizing the acidity of SO 3H-FSM, because the decomposition of SO 3H groups on SO 3H-FSM begins above 200 °C. An NH 3 adsorption microcalorimetric experiment at 150 °C shows that, compared with HZSM5, SO 3H-FSM has a smaller number of acid sites but has a similar number of strong acid sites with ammonia adsorption heat above 140 kJ mol −1. Comparison of the structural properties and catalytic results shows that a large pore diameter and low hydrophilicity are required to obtain high activity. Brønsted acid sites with a relatively strong acid strength are more suitable for this reaction, but the high acid concentration is not indispensable. The high activity of SO 3H-FSM should be caused by the presence of the strong Brønsted acid sites in the mesopore with a relatively low hydrophilicity, where both reactants can smoothly access the acid sites.