Accurate Measurements of NH3 Differential Adsorption Heat Unveil Structural Sensitivity of Brønsted Acid and Brønsted/Lewis Acid Synergy in Zeolites

Differential adsorption heats of NH3 on a series of zeolites, including MOR, MFI, FER, and BEA, are accurately measured to probe their acidity using flow-pulse adsorption microcalorimetry. Initial adsorption heats of NH3 at Brønsted acid sites (BAS) vary between 105 to 136 kJ/mol, depending on framework aluminum amounts and topography structures of zeolites. A Brønsted/Lewis acid synergy between BAS and proximate tricoordinated framework-associated aluminum species is identified to generate super acid sites with initial adsorption heats of NH3 around 150 kJ/mol, but occurs only in the MFI zeolites and sensitively depends on the Si/Al ratio. These accurate data of NH3 differential adsorption heats unveil structural sensitivity of BAS and Brønsted/Lewis acid synergy in zeolites and provide experimental benchmark data for fundamental understanding of acidity and acid-catalysis of zeolites.