Sulfonated Microporous Organic−Inorganic Hybrids as Strong Bronsted Acids1

• Published in: Journal of the American Chemical Society 2003-08, Vol.125 (34), p.10375-10383
• Main Authors: Wang, Zhike, Heising, Joy M, Clearfield, Abraham
• Format: Article
• Language: eng ; jpn
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja030226c

It has been discovered that the use of excess zirconium in reactions with 4,4‘-biphenyl and 4,4‘-terphenylbis(phosphonic acid) in DMSO or DMSO−ethanol mixtures produces microporous inorganic−organic hybrids. Surface areas of 400 m2/g and pore sizes in the range of 10−20 Å in diameter are routinely obtained. These materials are readily sulfonated with SO3 under pressure to yield strong Bronsted acids. The acid strength, measured by 13C NMR shifts of acetone and cyclopentanone in contact with the sulfonates, indicates an acidity close to that of 100% H2SO4. Condensation and cracking reactions were obtained for both ketones under mild conditions. A working hypothesis is presented to account for the high surface area and microporosity. The combination of high surface areas and pore dimensions that are between those of zeolites and mesoporous silicas commends these materials for applications in separations, ion exchange, and catalysis.