IR STUDIES OF ACIDITY OF ZEOLITES AND RELATED MATERIALS分子筛及相关材料酸性的研究.pdfVIP

IR STUDIES OF ACIDITY OF ZEOLITES AND RELATED MATERIALS Jerzy Datka Jagiellonian University Kraków FORMATION OF BRØNSTED ACID SITES IN ZEOLITES Me [(SiO ) (AlO ) ] Me [(SiO ) (AlO ) ] x/n 2 y 2 x x/n 2 y 2 x 1. Exchange Na+ → H+ + + + 0 2. Exchange Na → NH4 → H ( 300 C, vacuum) 3. Hydrolysis of cations: Mg2+ + H O ⇒ Mg(OH)+ + H+ 2 Ce3+ + H O ⇒Ce(OH)2+ + H+ 2 Ce(OH)2+ + H O ⇒Ce(OH) + + H+ 2 2 4. Reduction of metal ions Ni2+ + H ⇒ Ni 0 +H+ 2 5. Templates decomposition NATURE OF BRØNSTED ACID SITES IN ZEOLITES Bridging Si-(OH)-Al very strongly acidic IR maximum: 3500 – 3680 cm-1 Silanol groups Si-OH („terminal” OH) non acidic IR maximum: 3740 – 3750 cm-1 Al-OH groups (extraframework Al) non acidic IR maximum: ca. 3660 cm-1 Bronsted acid sites FORMATION OF LEWIS ACID SITES IN ZEOLITES 1. Extraframework Al (electronacceptor properties) weakly acidic 2. Dehydroxylation (condensation of two OH groups) strongly acidic 0 Dehydroxylation takes place at vacuum above 500 C OH GROUPS IN ZEOLITES HZSM-5 HY H-MOR OH groups ammonia adsorption pyridine adsorption PYRIDINE ADSORPTION IN H-MOR Two kinds of acidic Si-OH-Al groups: large channels